The invention relates to the acyl- and bisacylphosphine derivatives according to formula (I), wherein Y represents O, S, NR3, N—OR3 or N—NR3R4, Z represents O, S, NR3, N—OR3, N—NR3R4 or a free pair of electrons, and FG represents a leaving group and the remaining groups are defined as in the description. The invention further relates to a method for the production of the inventive derivatives and to their use.
##STR00001##
|
##STR00008##
where
R1, R2, R5, R6 and R7 are C1-C18-alkyl, or C2-C18-alkyl, C2-C18-alkenyl, C6-C12-aryl or C5-C12-cycloalkyl, each of which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, or are a five- to six-membered, oxygen, nitrogen and/or sulfur atom-containing heterocyclic radical, where the said radicals may each be substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
R2 is furthermore C1-C18-alkoxy, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, or is R1—(C═Y)—,
Y is O, S, NR3, N—OR3or N—NR3R4,
Z is O, S, NR3, N—OR3, N—NR3R4 or a free pair of electrons,
R3 is hydrogen, C1- to C4-alkyl, SO3H, phenyl or acetyl,
R4 is hydrogen, C1- to C4-alkyl, COOR3, or C6-C12-aryl or arylsulfonyl, each of which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
FG is a leaving group having the structure —F, —Cl, —I, —CN, —OCN, —SCN, —N+R6R7R8, —O(CO)R5, —O(CO)OR5, —O(SO)Cl, —O(SO2)Cl, —O(SO2)R5, —O(CO)Cl, —O(NO)OR5 or, in the case where Z≠S, —SR5,
R5 is furthermore C1-C18-alkoxy, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, and
R8 is C1-C18-alkyl, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, or C2-C18-alkyl, which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups,
from a substance of the formula (II)
##STR00009##
where
X is hydrogen or a cation,
which comprises reacting substance (II) with at least one agent which converts the —OX group into an —FG group.
##STR00015##
where
R1 is phenyl, α-naphthyl, β-naphthyl, 2-, 3- or 4-chlorophenyl, 2,6- or 2,4-dichlorophenyl, 2,4,6-trichlorophenyl, 2-, 3- or 4-methylphenyl, 2,6- or 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- or 4-ethylphenyl, 2,6- or 2,4-diethylphenyl, 2-, 3- or 4-iso-propylphenyl, 2-, 3- or 4-tert-butylphenyl, 2-, 3- or 4-methoxyphenyl, 2,6- or 2,4-dimethoxyphenyl, 2,6- or 2,4-diethoxyphenyl, methylnaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, cyclopentyl, cyclohexyl, 2,5-dimethylcyclopentyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-dimethoxycyclohexyl, 2,6-diethoxycyclohexyl, 2,6-dichlorocyclohexyl, 2,5-dichlorocyclopentyl, 2- or 3-furyl, 2- or 3-thiophenyl, 2- or 3-pyrryl, dimethylpyrryl or an ortho-substituted phenyl other than 2-methylphenyl, 2-methoxyphenyl or 2-chlorophenyl,
R5, R6 and R7 are C1-C18-alkyl, or C2-C18-alkyl, C2-C18-alkenyl, C6-C12-aryl or C5-C12-cycloalkyl, each of which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, or are a five- to six-membered, oxygen, nitrogen and/or sulfur atom-containing heterocyclic radical, where the said radicals may each be substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
Y is O, S, NR3, N—OR3 or N—NR3R4,
Z is O, S, NR3, N—OR3, N—NR3R4 or a free pair of electrons,
R3 is hydrogen, C1- to C4-alkyl, SO3H, phenyl or acetyl,
R4 is hydrogen, C1- to C4-alkyl, COOR3, or C6-C12-aryl or arylsulfonyl, each of which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
FG is a leaving group having the structure —Cl, —CN, —OCN, —SCN, —N+R6R7R8, —O(CO)R5, —O(CO)OR5, —O(SO)Cl, —O(SO2)OR5, —O(SO2)R5 or —O(CO)Cl,
R5 is furthermore C1-C18-alkoxy, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
R8 is C1-C18-alkyl, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, or C2-C18-alkyl, which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, and
R2 is ethoxy.
##STR00007##
where
R1 is α-naphthyl, β-naphthyl, 2-, 3- or 4-chlorophenyl, 2,6- or 2,4-dichlorophenyl, 2,4,6-trichlorophenyl, 2-, 3- or 4-methylphenyl, 2,6- or 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- or 4-ethylphenyl, 2,6- or 2,4-diethylphenyl, 2-, 3- or 4-iso-propylphenyl, 2-, 3- or 4-tert-butylphenyl, 2-, 3- or 4-methoxyphenyl, 2,6- or 2,4-dimethoxyphenyl, 2,6- or 2,4-diethoxyphenyl, methylnaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4-or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, cyclopentyl, cyclohexyl, 2,5-dimethylcyclopentyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-dimethoxycyclohexyl, 2,6-diethoxycyclohexyl, 2,6-dichlorocyclohexyl, 2,5-dichlorocyclopentyl, 2- or 3-furyl, 2- or 3-thiophenyl, 2- or 3-pyrryl, dimethylpyrryl or an ortho-substituted phenyl other than 2-methylphenyl, 2-methoxyphenyl or 2-chlorophenyl,
R2, R5, R6 and R7 are C1-C18-alkyl, or C2-C18-alkyl, C2-C18-alkenyl, C6-C12-aryl or C5-C12-cycloalkyl, each of which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, or are a five- to six-membered, oxygen, nitrogen and/or sulfur atom-containing heterocyclic radical, where the said radicals may each be substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
R2 is furthermore C1-C18-alkoxy, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, or is R1—(C═Y)—,
Y is O, S, NR3, N—OR3 or N—NR3R4,
Z is O, S, NR3, N—OR3, N—NR3R4 or a free pair of electrons,
R3 is hydrogen, C1- to C4-alkyl, SO3H, phenyl or acetyl,
R4 is hydrogen, C1- to C4-alkyl, COOR3, or C6-C12-aryl or arylsulfonyl, each of which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
FG is a leaving group having the structure —Cl, —CN, —OCN, —SCN, —N+R6R7R8, —O(CO)R5, —O(CO)OR5, —O(SO)Cl, —O(SO2)OR5, —O(SO2)R5 or —O(CO)Cl,
R5 is furthermore C1-C18-alkoxy, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, and
R8 is C1-C18-alkyl, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, or C2-C18-alkyl, which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups.
11. A photoinitiator mixture comprising at least one acyl- or bisacyiphosphine derivative of the formula (I)
##STR00012##
where
R1 is phenyl, α-naphthyl, β-naphthyl, 2-, 3- or 4-chlorophenyl, 2,6- or 2,4-dichlorophenyl, 2,4,6-trichlorophenyl, 2-, 3- or 4-methylphenyl, 2,6- or 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- or 4-ethylphenyl, 2,6- or 2,4-diethylphenyl, 2-, 3- or 4-iso-propylphenyl, 2-, 3- or 4-tert-butylphenyl, 2-, 3- or 4-methoxyphenyl, 2,6- or 2,4-dimethoxyphenyl, 2,6- or 2,4-diethoxyphenyl, methylnaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, cyclopentyl, cyclohexyl, 2,5-dimethylcyclopentyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-dimethoxycyclohexyl, 2,6-diethoxycyclohexyl, 2,6-dichlorocyclohexyl, 2,5-dichlorocyclopentyl, 2- or 3-furyl, 2- or 3-thiophenyl, 2- or 3-pyrryl, dimethylpyrryl or an ortho-substituted phenyl other than 2-methylphenyl, 2-methoxyphenyl or 2-chlorophenyl,
R2, R5, R6 and R7 are C1-C18-alkyl, or C2-C18-alkyl, C2-C18-alkenyl, C6-C12-aryl or C5-C12-cycloalkyl, each of which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, or are a five- to six-membered, oxygen, nitrogen and/or sulfur atom-containing heterocyclic radical, where the said radicals may each be substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
R2 is furthermore which is unsubstituted substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, or is R1—(C═Y)—,
Y is O, S, NR3, N—OR3 or N—NR3R4,
Z is O, S, NR3, N—OR3, N—NR3R4 or a free pair of electrons,
R3 is hydrogen, C1- to C4-alkyl, SO3H, phenyl or acetyl,
R4 is hydrogen, C1- to C4-alkyl, COOR3, or C6-C12-aryl or arylsulfonyl, each of which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
FG is a leaving group having the structure —Cl, —CN, —OCN, —SCN, —N+R6R7R8, —O(CO)R5, —O(CO)OR5, —O(SO)Cl, —O(SO2)OR5, —O(SO2)R5 or —O(CO)Cl,
R5 is furthermore C1-C18-alkoxy, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, and
R8 is C1-C18-alkyl, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, or C2-C18-alkyl, which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups.
12. A radiation-curable composition comprising at least one acyl- or bisacyiphosphine derivative of the formula (I)
##STR00013##
where
R1 is phenyl, α-naphthyl, β-naphthyl, 2-, 3- or 4-chlorophenyl, 2,6- or 2,4-dichlorophenyl, 2,4,6-trichlorophenyl, 2-, 3- or 4-methylphenyl, 2,6- or 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- or 4-ethylphenyl, 2,6- or 2,4-diethylphenyl, 2-, 3- or 4-iso-propylphenyl, 2-, 3- or 4-tert-butylphenyl, 2-, 3- or 4-methoxyphenyl, 2,6- or 2,4-dimethoxyphenyl, 2,6- or 2,4-diethoxyphenyl, methylnaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, cyclopentyl, cyclohexyl, 2,5-dimethylcyclopentyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-dimethoxycyclohexyl, 2,6-diethoxycyclohexyl, 2,6-dichlorocyclohexyl, 2,5-dichlorocyclopentyl, 2- or 3-furyl, 2- or 3-thiophenyl, 2- or 3-pyrryl, dimethylpyrryl or an ortho-substituted phenyl other than 2-methylphenyl, 2-methoxyphenyl or 2-chlorophenyl,
R2, R5, R6 and R7 are C1-C18-alkyl, or C2-C18-alkyl, C2-C18-alkenyl, C6-C12-aryl or C5-C12-cycloalkyl, each of which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, or are a five- to six-membered, oxygen, nitrogen and/or sulfur atom-containing heterocyclic radical, where the said radicals may each be substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
R2 is furthermore which is unsubstituted substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, or is R1—(C═Y)—,
Y is O, S, NR3, N—OR3 or N—NR3R4,
Z is O, S, NR3, N—OR3, N—NR3R4 or a free pair of electrons,
R3 is hydrogen, C1- to C4-alkyl, SO3H, phenyl or acetyl,
R4 is hydrogen, C1- to C4-alkyl, COOR3, or C6-C12-aryl or arylsulfonyl, each of which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
FG is a leaving group having the structure —Cl, —CN, —OCN, —SCN, —N+R6R7R8, —O(CO)R5, —O(CO)OR5, —O(SO)Cl, —O(SO2)OR5, —O(SO2)R5 or —O(CO)Cl,
R5 is furthermore C1-C18-alkoxy, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, and
R8 is C1-C18-alkyl, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, or C2-C18-alkyl, which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups.
10. A method of photoinitiation comprising photoinitiating a potopolymerizable compositions with an acyl- or bisacylphosphine derivative of the formula (I)
##STR00011##
where
R1 is phenyl, α-naphthyl, β-naphthyl, 2-, 3- or 4-chlorophenyl, 2,6- or 2,4-dichlorophenyl, 2,4,6-trichlorophenyl, 2-, 3- or 4-methylphenyl, 2,6- or 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- or 4-ethylphenyl, 2,6- or 2,4-diethylphenyl, 2-, 3- or 4-iso-propylphenyl, 2-, 3- or 4-tert-butylphenyl, 2-, 3- or 4-methoxyphenyl, 2,6- or 2,4-dimethoxyphenyl, 2,6- or 2,4-diethoxyphenyl, methylnaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, cyclopentyl, cyclohexyl, 2,5-dimethylcyclopentyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-dimethoxycyclohexyl, 2,6-diethoxycyclohexyl, 2,6-dichlorocyclohexyl, 2,5-dichlorocyclopentyl, 2- or 3-furyl, 2- or 3-thiophenyl, 2- or 3-pyrryl, dimethylpyrryl or an ortho-substituted phenyl other than 2-methylphenyl, 2-methoxyphenyl or 2-chlorophenyl,
R2, R5, R6 and R7 are C1-C18-alkyl, or C2-C18-alkyl, C2-C18-alkenyl, C6-C12-aryl or C5-C12-cycloalkyl, each of which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, or are a five- to six-membered, oxygen, nitrogen and/or sulfur atom-containing heterocyclic radical, where the said radicals may each be substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
R2 is furthermore which is unsubstituted substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, or is R1—(C═Y)—,
Y is O, S, NR3, N—OR3 or N—NR3R4,
Z is O, S, NR3, N—OR3, N—NR3R4 or a free pair of electrons,
R3 is hydrogen, C1- to C4-alkyl, SO3H, phenyl or acetyl,
R4 is hydrogen, C1- to C4-alkyl, COOR3, or C6-C12-aryl or arylsulfonyl, each of which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
R5 is furthermore C1-C18-alkoxy, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
R8 is C1-C18-alkyl, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, or C2-C18-alkyl, which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, and
FG is defined as follows:
FG —Br, —(NR3)—NR4R9, —(NR3)—OR9 or —SR3 (for Z=S), and
R9 is hydrogen or C1- to C4-alkyl.
9. A method of photoinitiation comprising photoinitiating a potopolymerizable compositions with an acyl- or bisacylphosphine derivative of the formula (I)
##STR00010##
where
R1 is phenyl, α-naphthyl, β-naphthyl, 2-, 3- or 4-chlorophenyl, 2,6- or 2,4-dichlorophenyl, 2,4,6-trichlorophenyl, 2-, 3- or 4-methylphenyl, 2,6- or 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- or 4-ethylphenyl, 2,6- or 2,4-diethylphenyl, 2-, 3- or 4-iso-propylphenyl, 2-, 3- or 4-tert-butylphenyl, 2-, 3- or 4-methoxyphenyl, 2,6- or 2,4-dimethoxyphenyl, 2,6- or 2,4-diethoxyphenyl, methylnaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, cyclopentyl, cyclohexyl, 2,5-dimethylcyclopentyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-dimethoxycyclohexyl, 2,6-diethoxycyclohexyl, 2,6-dichlorocyclohexyl, 2,5-dichlorocyclopentyl, 2- or 3-furyl, 2- or 3-thiophenyl, 2- or 3-pyrryl, dimethylpyrryl or an ortho-substituted phenyl other than 2-methylphenyl, 2-methoxyphenyl or 2-chlorophenyl,
R2, R5 and R7 are C1-C18-alkyl, or C2-C18-alkyl, C2-C18-alkenyl, C6-C12-aryl or C5-C12-cycloalkyl, each of which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, or are a five- to six-membered, oxygen, nitrogen and/or sulfur atom-containing heterocyclic radical, where the said radicals may each be substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
R2 is furthermore C1-C18-alkoxy is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocylic radicals, or is R1—(C═Y)—,
Y is O, S, NR3, N—OR3 or N—NR3R4,
Z is O, S, NR3, N—OR3, N—NR3R4 or a free pair of electrons,
R3 is hydrogen, C1- to C4-alkyl, SO3H, phenyl or acetyl,
R4 is hydrogen, C1- to C4-alkyl, COOR3, or C6-C12-aryl or arylsulfonyl, each of which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
FG is a leaving group having the structure —Cl, —CN, —OCN, —SCN, —N+R6R7R8, —O(CO)R5, —O(CO)OR5, —O(SO)Cl, —O(SO2)OR5, —O(SO2)R5 or —O(CO)Cl,
R5 is furthermore C1-C18-alkoxy, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, and
R8 is C1-C18-alkyl, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, or C2-C18-alkyl, which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups.
13. A radiation-curable composition obtainable by reaction of at least one acyl- or bisacylphosphine derivative of the formula (I)
##STR00014##
where
R1 is phenyl, α-naphthyl, β-naphthyl, 2-, 3- or 4-chlorophenyl, 2,6- or 2,4-dichlorophenyl, 2,4,6-trichlorophenyl, 2-, 3- or 4-methylphenyl, 2,6- or 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- or 4-ethylphenyl, 2,6- or 2,4-diethylphenyl, 2-, 3- or 4-iso-propylphenyl, 2-, 3- or 4-tert-butylphenyl, 2-, 3- or 4-methoxyphenyl, 2,6- or 2,4-dimethoxyphenyl, 2,6- or 2,4-diethoxyphenyl, methylnaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, cyclopentyl, cyclohexyl, 2,5-dimethylcyclopentyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-dimethoxycyclohexyl, 2,6-diethoxycyclohexyl, 2,6-dichlorocyclohexyl, 2,5-dichlorocyclopentyl, 2- or 3-furyl, 2- or 3-thiophenyl, 2- or 3-pyrryl, dimethylpyrryl or an ortho-substituted phenyl other than 2-methylphenyl, 2-methoxyphenyl or 2-chlorophenyl,
R2, R5, R6 and R7 are C1-C18-alkyl, or C2-C18-alkyl, C2-C18-alkenyl, C6-C12-aryl or C5-C12-cycloalkyl, each of which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, or are a five- to six-membered, oxygen, nitrogen and/or sulfur atom-containing heterocyclic radical, where the said radicals may each be substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
R2 is furthermore which is unsubstituted substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, or is R1—(C═Y)—,
Y is O, S, NR3, N—OR3 or N—NR3R4,
Z is O, S, NR3, N—OR3, N—NR3R4 or a free pair of electrons,
R3 is hydrogen, C1- to C4-alkyl, SO3H, phenyl or acetyl,
R4 is hydrogen, C1- to C4-alkyl, COOR3, or C6-C12-aryl or arylsulfonyl, each of which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals,
FG is a leaving group having the structure —Cl, —CN, —OCN, —SCN, —N+R6R7R8, —O(CO)R5, —O(CO)OR5, —O(SO)Cl, —O(SO2)OR5, —O(SO2)R5 or —O(CO)Cl,
R5 is furthermore C1-C18-alkoxy, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, and
R8 is C1-C18-alkyl, which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, or C2-C18-alkyl, which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups,
with a compound containing free hydroxyl, amino, monoalkylamino, monoarylamino and/or mercapto groups.
2. An acyl- or bisacylphosphine derivative as claimed in
Y is O, S or NR3,
Z is O, S, NR3 or a free pair of electrons,
FG is —Cl, —O(CO)R5, —O(CO)OR5, —O(SO)Cl, —O(SO2)R5 or —O(CO)Cl.
3. An acyl- or bisacylphosphine derivative as claimed in
Y is O or S,
Z is O, S or a free pair of electrons,
FG is —Cl, —O(CO)R5, —O(CO)OR5 or —O(SO2)R5.
4. An acyl- or bisacylphosphine derivative as claimed in
Y is O,
Z is O or a free pair of electrons,
FG is —Cl or —O(SO2)R5.
5. An acyl- or bisacylphosphine derivative as claimed in
R1 is 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, or 2,4,6-trichlorophenyl, and
R2 is phenyl or ethoxy.
7. A process as claimed in
8. A process as claimed in
14. A radiation-curable composition as claimed in
16. An acyl- or bisacylphosphine derivative as claimed in
R1 is 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl or 2,4,6-trichlorophenyl, and
R2 is phenyl or ethoxy.
17. An acyl- or bisacylphosphine derivative as claimed in
R1 is 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl or 2,4,6-trichlorophenyl, and
R2 is phenyl or ethoxy.
18. An acyl- or bisacylphosphine derivative as claimed in
R1 is 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl or 2,4,6-trichlorophenyl, and
R2 is phenyl or ethoxy.
|
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The present invention relates to reactive acyl- and bisacylphosphine derivatives, to a process for their preparation, and to their use.
Acyl- and bisacylphosphine oxides and the use thereof as photoinitiators have been known for some time.
JP 10-62927, JP 9-152689, EP-A 724 194 and JP 3-10241 disclose compounds having a phosphine oxide structure which carry a hydroxylamino or alkoxylamino group or a hydrazido group on the central phosphorus atom and which are used in photographic materials.
U.S. Pat. No. 5,683,615 discloses magnetorheological liquids which comprise dialkyl dithiophosphates.
Also known are derivatives of acylphosphine oxides, for example those which carry an unsubstituted or substituted amino group, a hydroxyl group or an —O-M+ group, where M+ is an equivalent of a cation, on the central phosphorus atom (EP-A 62 839), a C1-C12-alkoxy group (DE-A 196 50 562), an aryloxy group (EP-A 600 373) or a silyloxy group (EP-A 487 453), and which can likewise be used as photoinitiators.
Many of the photoinitiators used hitherto have the problem that residues or degradation products of photoinitiators are able to diffuse out of the cured coating into the surrounding medium (migration), where they can cause problems, for example if the medium is a packaging material for foods.
Furthermore, the low solubility and incorporation ability of certain phosphine oxides are limited, which means that there continues to be a demand for other phosphine oxides having improved interactions for radiation-curable surface-coating systems.
There continues to be a demand in free-radical polymerization for highly reactive photoinitiator systems which are easy to prepare and easy to handle. Furthermore, such systems should be thermally stable and stable on storage.
EP-B 7 508 discloses the synthesis of acylphosphine oxides in an Arbusov rearrangement by reaction of alkoxyphosphines and acid chlorides:
##STR00002##
where p-Tol=4-methylphenyl, and Ph=phenyl.
U.S. Pat. No. 5,472,992 discloses the synthesis of bisacylphosphines in which a phosphine is diacylated in the presence of a base and subsequently oxidized.
However, these synthetic methods have the disadvantage that volatile, toxic and foul-smelling phosphines have to be used.
WO 00/32612 furthermore discloses the synthesis of acyl- and bisacylphosphines in which an organic phosphoryl halide is brought into contact with an alkali metal or magnesium/lithium, and the resultant metallated phosphines are then reacted with an acid chloride:
##STR00003##
where Ph=phenyl and Ar=aryl.
However, a reaction of this type requires complex handling of, for example, metallic lithium for the metallation.
A common feature of these syntheses is that they are restricted by their substrates, and the products can thus only be varied in narrow limits.
It is an object of the present invention to provide compounds which enable the simple synthesis of novel acyl- and bisacylphosphine derivatives having a high tolerance to functional groups and which can themselves likewise be employed as photoinitiators with a very low tendency to migrate.
We have found that this object is achieved by acyl- or bisacylphosphine derivatives of the formula (I)
##STR00004##
where
In these formulae,
C1-C18-alkyl which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, α,α-dimethylbenzyl, benzhydryl, p-tolylmethyl, 1-(p-butylphenyl)ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di(methoxycarbonyl)ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, chloromethyl, 2-chloroethyl, trichloromethyl, trifluoromethyl, 1,1-dimethyl-2-chloroethyl, 2-methoxyisopropyl, 2-ethoxyethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 2,2,2-trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl or 6-ethoxyhexyl,
C1-C18-alkoxy which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals is, for example, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, 6-hydroxy-1,4-dioxohexyl, 9-hydroxy-1,4,7-trioxononyl, 12-hydroxy-1,4,7,10-tetraoxododecyl, 6-methoxy-1,4-dioxohexyl, 9-methoxy-1,4,7-trioxononyl, 12-methoxy-1,4,7,10-tetraoxododecyl, 6-ethoxy-1,4-dioxohexyl, 9-ethoxy-1,4,7-trioxononyl, 12-ethoxy-1,4,7,10-tetraoxododecyl, 8-hydroxy-1,5-dioxooctyl, 12-hydroxy-1,5,9-trioxooctyl, 16-hydroxy-1,5,9,13-tetraoxohexadecyl, 8-methoxy-1,5-dioxooctyl, 12-methoxy-1,5,9-trioxooctyl, 16-methoxy-1,5,9,13-tetraoxohexadecyl, 8-ethoxy-1,5-dioxooctyl, 12-ethoxy-1,5,9-trioxooctyl, 16-ethoxy-1,5,9,13-tetraoxohexadecyl, 10-hydroxy-1,6-dioxodecyl, 15-hydroxy-1,6,11-trioxopentadecyl, 10-methoxy-1,6-dioxodecyl, 15-methoxy-1,6,11-trioxopentadecyl, 10-ethoxy-1,6-dioxodecyl or 15-ethoxy-1,6,11-trioxopentadecyl,
C2-C18-alkyl which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups is, for example, 5-hydroxy-3-oxapentyl, 8-hydroxy-3,6-dioxaoctyl, 11-hydroxy-3,6,9-trioxaundecyl, 7-hydroxy-4-oxaheptyl, 11-hydroxy-4,8-dioxaundecyl, 15-hydroxy-4,8,12-trioxapentadecyl, 9-hydroxy-5-oxanonyl, 14-hydroxy-5,10-oxatetradecyl, 5-methoxy-3-oxapentyl, 8-methoxy-3,6-dioxaoctyl, 11-methoxy-3,6,9-trioxaundecyl, 7-methoxy-4-oxaheptyl, 11-methoxy-4,8-dioxaundecyl, 15-methoxy-4,8,12-trioxapentadecyl, 9-methoxy-5-oxanonyl, 14-methoxy-5,10-oxatetradecyl, 5-ethoxy-3-oxapentyl, 8-ethoxy-3,6-dioxaoctyl, 11-ethoxy-3,6,9-trioxaundecyl, 7-ethoxy-4-oxaheptyl, 11-ethoxy-4,8-dioxaundecyl, 15-ethoxy-4,8,12-trioxapentadecyl, 9-ethoxy-5-oxanonyl or 14-ethoxy-5,10-oxatetradecyl.
The number of oxygen atoms and/or sulfur atoms and/or imino groups is unrestricted. In general, it is not more than 5 in the radical, preferably not more than 4 and very particularly preferably not more than 3.
Furthermore, at least one carbon atom, preferably at least two carbon atoms, are located between two heteroatoms.
Substituted and unsubstituted imino groups can be, for example, imino, methylimino, iso-propylimino, n-butylimino or tert-butylimino.
Furthermore,
C2-C18-alkenyl which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals is, for example, vinyl, 1-propenyl, allyl, methallyl, 1,1-dimethylallyl, 2-butenyl, 2-hexenyl, octenyl, undecenyl, dodecenyl, octadecenyl, 2-phenylvinyl, 2-methoxyvinyl, 2-ethoxyvinyl, 2-methoxyallyl, 3-methoxyallyl, 2-ethoxyallyl, 3-ethoxyallyl or 1- or 2-chlorovinyl,
C6-C12-aryl which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals is, for example, phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-biphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl or ethoxymethylphenyl,
C5-C12-cycloalkyl which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals is, for example, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl and a saturated or unsaturated bicyclic system, for example norbornyl or norbornenyl,
a five- to six-membered, oxygen, nitrogen and/or sulfur atom-containing heterocyclic radical is, for example, furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl,
C1 to C4-alkyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, and
C6-C12-aryl or arylsulfonyl, each which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, is, for example, phenyl, 2,6-dinitrophenyl, 2,4-dinitrophenyl, 2-nitrophenyl, 4-nitrophenyl, formyl, acetyl, propionyl, carbamoyl, phenylsulfonyl or 4-methylphenylsulfonyl.
The number of substituents in the stated radicals is unrestricted. In general, it is up to 3 substituents, preferably up to 2 substituents and particularly preferably up to one substituent, in radicals having from one to three carbon atoms. In radicals having from four to six carbon atoms, it is generally up to 4 substituents, preferably up to 3 substituents and particularly preferably up to one substituent. In radicals having more than seven carbon atoms, it is generally up to 6 substituents, preferably up to 4 substituents and particularly preferably up to two substituents.
R1 is preferably phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 2-, 3- or 4-chlorophenyl, 2,6- or 2,4-dichlorophenyl, 2,4,6-trichlorophenyl, 2-, 3- or 4-methylphenyl, 2,6- or 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- or 4-ethylphenyl, 2,6- or 2,4-diethylphenyl, 2-, 3- or 4-iso-propylphenyl, 2-, 3- or 4-tert-butylphenyl, 2-, 3- or 4-methoxyphenyl, 2,6- or 2,4-dimethoxyphenyl, 2,6- or 2,4-diethoxyphenyl, methylnaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, cyclopentyl, cyclohexyl, 2,5-dimethylcyclopentyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-dimethoxycyclohexyl, 2,6-diethoxycyclohexyl, 2,6-dichlorocyclohexyl, 2,5-dichlorocyclopentyl, 2- or 3-furyl, 2- or 3-thiophenyl, 2- or 3-pyrryl, dimethylpyrryl or ortho-substituted phenyls, such as 2-methylphenyl, 2-methoxyphenyl or 2-chlorophenyl.
R1 is particularly preferably phenyl, tolyl, α-naphthyl, β-naphthyl, 2,6- or 2,4-dichlorophenyl, 2,4,6-trichlorophenyl, 2,6- or 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6- or 2,4-diethylphenyl, 2-iso-propylphenyl, 2-tert-butylphenyl, 2,6- or 2,4-dimethoxyphenyl, 2,6- or 2,4-diethoxyphenyl, methylnaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 2,6-dinitrophenyl, 2,5-dimethylcyclopentyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-dimethoxycyclohexyl, 2,6-diethoxycyclohexyl, 2,6-dichlorocyclohexyl, 2,5-dichlorocyclopentyl, 2-methylphenyl, 2-methoxyphenyl or 2-chlorophenyl.
R1 is very particularly preferably phenyl, α-naphthyl, 2,6-dichlorophenyl, 2,4,6-trichlorophenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diethylphenyl, 2,6-dimethoxyphenyl, 2,6-diethoxyphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 2,6-dinitrophenyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-dimethoxycyclohexyl, 2,6-diethoxycyclohexyl or 2,6-dichlorocyclohexyl.
R1 is in particular phenyl, 2,6-dichlorophenyl, 2,4,6-trichlorophenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl or 2,6-dimethoxyphenyl.
R2 is preferably 2,4,4-trimethylpentyl, benzyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, 6-hydroxy-1,4-dioxohexyl, 9-hydroxy-1,4,7-trioxononyl, 12-hydroxy-1,4,7,10-tetraoxododecyl, 6-methoxy-1,4-dioxohexyl, 9-methoxy-1,4,7-trioxononyl, 12-methoxy-1,4,7,10-tetraoxododecyl, 6-ethoxy-1,4-dioxohexyl, 9-ethoxy-1,4,7-trioxononyl, 12-ethoxy-1,4,7,10-tetraoxododecyl, 8-hydroxy-1,5-dioxooctyl, 12-hydroxy-1,5,9-trioxooctyl, 16-hydroxy-1,5,9,13-tetraoxohexadecyl, 10-hydroxy-1,6-dioxodecyl, 15-hydroxy-1,6,11-trioxopentadecyl, vinyl, 1-propenyl, allyl, methallyl, 1,1-dimethylallyl, 2-butenyl, 2-hexenyl, 2-phenylvinyl, 2-methoxyvinyl, 2-ethoxyvinyl, 2-chlorovinyl, phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-biphenylyl, 2-, 3- or 4-chlorophenyl, 2,4- or 2,6-dichlorophenyl, 2,4,6-trichlorophenyl, 2-, 3- or 4-methylphenyl, 2,4- or 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- or 4-ethylphenyl, 2,4- or 2,6-diethylphenyl, 2-, 3- or 4-iso-propylphenyl, 2-, 3- or 4-tert-butylphenyl, 2-, 3- or 4-methoxyphenyl, 2,4- or 2,6-dimethoxyphenyl, 2-, 3- or 4-ethoxyphenyl, methylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,4- or 2,6-dimethoxyphenyl, 2,4- or 2,6-dichlorophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl or R1—(C═Y)—.
R2 is particularly preferably benzyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, 6-hydroxy-1,4-dioxohexyl, 9-hydroxy-1,4,7-trioxononyl, 12-hydroxy-1,4,7,10-tetraoxododecyl, 6-methoxy-1,4-dioxohexyl, 9-methoxy-1,4,7-trioxononyl, 12-methoxy-1,4,7,10-tetraoxododecyl, 6-ethoxy-1,4-dioxohexyl, 9-ethoxy-1,4,7-trioxononyl, 12-ethoxy-1,4,7,10-tetraoxododecyl, 8-hydroxy-1,5-dioxooctyl, 12-hydroxy-1,5,9-trioxooctyl, 16-hydroxy-1,5,9,13-tetraoxohexadecyl, 10-hydroxy-1,6-dioxodecyl, 15-hydroxy-1,6,11-trioxopentadecyl, vinyl, 2-butenyl, 2-phenylvinyl, phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-biphenylyl, 2-, 3- or 4-chlorophenyl, 2,4- or 2,6-dichlorophenyl, 2,4,6-trichlorophenyl, 2-, 3- or 4-methylphenyl, 2,4- or 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- or 4-ethylphenyl, 2-, 3- or 4-iso-propylphenyl, 2-, 3- or 4-tert-butylphenyl, 2-, 3- or 4-methoxyphenyl, 2,4- or 2,6-dimethoxyphenyl, 2-, 3- or 4-ethoxyphenyl, methylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl or R1—(C═Y)—.
R2 is very particularly preferably methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, sec-butoxy, iso-butoxy, tert-butoxy, 6-hydroxy-1,4-dioxohexyl, 9-hydroxy-1,4,7-trioxononyl, 12-hydroxy-1,4,7,10-tetraoxododecyl, 8-hydroxy-1,5-dioxooctyl, 12-hydroxy-1,5,9-trioxooctyl, 16-hydroxy-1,5,9,13-tetraoxohexadecyl, 10-hydroxy-1,6-dioxodecyl, 15-hydroxy-1,6,11-trioxopentadecyl, phenyl, xylyl, α-naphthyl, β-naphthyl, 4-biphenylyl, 2-, 3- or 4-chlorophenyl, 2,4-dichlorophenyl, 2-, 3- or 4-methylphenyl, 2,4-dimethylphenyl, 2-, 3- or 4-ethylphenyl, 2-, 3- or 4-methoxyphenyl, 2,4-dimethoxyphenyl, 2-, 3- or 4-ethoxyphenyl, methylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2- or 4-nitrophenyl or R1—(C═Y)—.
Y is preferably O, S or NR3.
Y is particularly preferably O or S and very particularly preferably O.
Z is preferably O, S, NR3 or a free pair of electrons, particularly preferably O, S or a free pair of electrons, very particularly preferably O or S and in particular O.
R3 is preferably hydrogen, methyl, tert-butyl, phenyl or SO3H, particularly preferably hydrogen, tert-butyl, phenyl or SO3H and very particularly preferably hydrogen, tert-butyl or phenyl.
R4 is preferably hydrogen, methyl, phenyl, 2,4-dinitrophenyl, carbamoyl, phenylsulfonyl or 4-methylphenylsulfonyl, particularly preferably hydrogen, phenyl, 2,4-dinitrophenyl or phenylsulfonyl, very particularly preferably hydrogen, 2,4-dinitrophenyl or phenylsulfonyl and in particular hydrogen or 2,4-dinitrophenyl.
FG is preferably —Cl, —CN, —OCN, —SCN, —N+R6R7R8, —O(CO)R5, —O(CO)OR5, —(SO)Cl, —(SO2)R5, —(SO2)OR5 or —O(CO)Cl.
FG is particularly preferably —Cl, —CN, —OCN, —SCN, —N+R6R7R8, —O(CO)R5, —O(CO)OR5 or —(SO2)R5.
FG is very particularly preferably —Cl, —O(CO)R5, —O(CO)OR5 or —(SO2)R5 and in particular —Cl or —(SO2)R5.
R5 is preferably methoxy, ethoxy, n-propoxy, n-butoxy, methyl, ethyl, n-propyl, n-butyl, tert-butyl, phenyl, 4-methylphenyl, trifluoromethyl or 4-bromophenyl.
R5 is particularly preferably methoxy, ethoxy, n-butoxy, methyl, ethyl, n-butyl, phenyl, 4-methylphenyl, trifluoromethyl or 4-bromophenyl.
R5 is very particularly preferably n-butoxy, methyl, ethyl, n-butyl, phenyl or 4-methylphenyl and in particular methyl or 4-methylphenyl.
R6, R7 and R8, independently of one another, are preferably methyl, ethyl, n-propyl, n-butyl, benzyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl or 2-butoxycarbonylethyl.
R6, R7 and R8, independently of one another, are particularly preferably methyl, benzyl, 2-hydroxyethyl, 2-cyanoethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl or 2-butoxycarbonylethyl.
R6, R7 and R8, independently of one another, are very particularly preferably methyl, benzyl, 2-hydroxyethyl or 2-butoxycarbonylethyl and in particular methyl, 2-hydroxyethyl or 2-butoxycarbonylethyl.
Of the compounds described by the formula (I), particular preference is given to the following species I-1 to I-372, in which the radicals in the formula (I) have the following meanings:
I-
R1
R2
Y
Z
FG
1
TMP
Ph
O
O
Cl
2
TMP
Ph
O
O
I
3
TMP
Ph
O
O
OCN
4
TMP
Ph
O
O
SCN
5
TMP
Ph
O
O
CN
6
TMP
Ph
O
O
Acetoxy (—O(CO)CH3)
7
TMP
Ph
O
O
Benzoyloxy (—O(CO)Ph)
8
TMP
Ph
O
O
Formyloxy (—O(CO)H)
9
TMP
Ph
O
O
Methoxycarbonyloxy (—O(CO)OCH3)
10
TMP
Ph
O
O
Ethoxycarbonyloxy (—O(CO)OCH2CH3)
11
TMP
Ph
O
O
n-Butoxycarbonyloxy (—O(CO)OCH2CH2CH2CH3)
12
TMP
Ph
O
O
Chlorocarbonyloxy (—O(CO)Cl)
13
TMP
Ph
O
O
Chlorosulfinyloxy (—O(SO)Cl)
14
TMP
Ph
O
O
Methoxysulfinyloxy (—O(SO)OCH3)
15
TMP
Ph
O
O
Ethoxysulfinyloxy (—O(SO)OCH2CH3)
16
TMP
Ph
O
O
n-Butoxysulfinyloxy (—O(SO)OCH2CH2CH2CH3)
17
TMP
Ph
O
O
Chlorosulfuryloxy (—O(SO2)Cl)
18
TMP
Ph
O
O
Methoxysulfuryloxy (—O(SO2)OCH3)
19
TMP
Ph
O
O
Ethoxysulfuryloxy (—O(SO2)OCH2CH3)
20
TMP
Ph
O
O
Methylsulfonyloxy (—O(SO2)CH3)
21
TMP
Ph
O
O
Trifluoromethylsulfonyloxy (—O(SO2)CF3)
22
TMP
Ph
O
O
Benzenesulfonyloxy (—O(SO2)Ph)
23
TMP
Ph
O
O
p-Toluenesulfonyloxy (—O(SO2)Ph-4-CH3)
24
TMP
Ph
O
O
Dodecylbenzenesulfonyloxy
25
TMP
Ph
O
O
p-Bromobenzenesulfonyloxy
(—O(SO2)Ph-4-Br)
26
TMP
Ph
O
O
Diethyl(2-hydroxyethyl)ammonium
27
TMP
Ph
O
O
Benzyldiethylammonium
28
TMP
Ph
O
O
Tris(2-hydroxyethyl)ammonium
29
TMP
Ph
O
O
Dimethyl(2-hydroxyethyl)ammonium
30
TMP
Ph
O
O
Benzyldimethylammonium
31
TMP
Ph
O
O
Trimethylammonium
32
TMP
OEt
O
O
Cl
33
TMP
OEt
O
O
I
34
TMP
OEt
O
O
OCN
35
TMP
OEt
O
O
SCN
36
TMP
OEt
O
O
CN
37
TMP
OEt
O
O
Acetoxy (—O(CO)CH3)
38
TMP
OEt
O
O
Benzoyloxy (—O(CO)Ph)
39
TMP
OEt
O
O
Formyloxy (—O(CO)H)
40
TMP
OEt
O
O
Methoxycarbonyloxy (—O(CO)OCH3)
41
TMP
OEt
O
O
Ethoxycarbonyloxy (—O(CO)OCH2CH3)
42
TMP
OEt
O
O
n-Butoxycarbonyloxy (—O(CO)OCH2CH2CH2CH3)
43
TMP
OEt
O
O
Chlorocarbonyloxy (—O(CO)Cl)
44
TMP
OEt
O
O
Chlorosulfinyloxy (—O(SO)Cl)
45
TMP
OEt
O
O
Methoxysulfinyloxy (—O(SO)OCH3)
46
TMP
OEt
O
O
Ethoxysulfinyloxy (—O(SO)OCH2CH3)
47
TMP
OEt
O
O
n-Butoxysulfinyloxy (—O(SO)OCH2CH2CH2CH3)
48
TMP
OEt
O
O
Chlorosulfuryloxy (—O(SO2)Cl)
49
TMP
OEt
O
O
Methoxysulfuryloxy (—O(SO2)OCH3)
50
TMP
OEt
O
O
Ethoxysulfuryloxy (—O(SO2)OCH2CH3)
51
TMP
OEt
O
O
Methylsulfonyloxy (—O(SO2)CH3)
52
TMP
OEt
O
O
Trifluoromethylsulfonyloxy (—O(SO2)CF3)
53
TMP
OEt
O
O
Benzenesulfonyloxy (—O(SO2)Ph)
54
TMP
OEt
O
O
p-Toluenesulfonyloxy (—O(SO2)Ph-4-CH3)
55
TMP
OEt
O
O
Dodecylbenzenesulfonyloxy
56
TMP
OEt
O
O
p-Bromobenzenesulfonyloxy
(—O(SO2)Ph-4-Br)
57
TMP
OEt
O
O
Diethyl(2-hydroxyethyl)ammonium
58
TMP
OEt
O
O
Benzyldiethylammonium
59
TMP
OEt
O
O
Tris(2-hydroxyethyl)ammonium
60
TMP
OEt
O
O
Dimethyl(2-hydroxyethyl)ammonium
61
TMP
OEt
O
O
Benzyldimethylammonium
62
TMP
OEt
O
O
Trimethylammonium
63
TMP
TMB
O
O
Cl
64
TMP
TMB
O
O
I
65
TMP
TMB
O
O
OCN
66
TMP
TMB
O
O
SCN
67
TMP
TMB
O
O
CN
68
TMP
TMB
O
O
Acetoxy (—O(CO)CH3)
69
TMP
TMB
O
O
Benzoyloxy (—O(CO)Ph)
70
TMP
TMB
O
O
Formyloxy (—O(CO)H)
71
TMP
TMB
O
O
Methoxycarbonyloxy (—O(CO)OCH3)
72
TMP
TMB
O
O
Ethoxycarbonyloxy (—O(CO)OCH2CH3)
73
TMP
TMB
O
O
n-Butoxycarbonyloxy (—O(CO)OCH2CH2CH2CH3)
74
TMP
TMB
O
O
Chlorocarbonyloxy (—O(CO)Cl)
75
TMP
TMB
O
O
Chlorosulfinyloxy (—O(SO)Cl)
76
TMP
TMB
O
O
Methoxysulfinyloxy (—O(SO)OCH3)
77
TMP
TMB
O
O
Ethoxysulfinyloxy (—O(SO)OCH2CH3)
78
TMP
TMB
O
O
n-Butoxysulfinyloxy (—O(SO)OCH2CH2CH2CH3)
79
TMP
TMB
O
O
Chlorosulfuryloxy (—O(SO2)Cl)
80
TMP
TMB
O
O
Methoxysulfuryloxy (—O(SO2)OCH3)
81
TMP
TMB
O
O
Ethoxysulfuryloxy (—O(SO2)OCH2CH3)
82
TMP
TMB
O
O
Methylsulfonyloxy (—O(SO2)CH3)
83
TMP
TMB
O
O
Trifluoromethylsulfonyloxy (—O(SO2)CF3)
84
TMP
TMB
O
O
Benzenesulfonyloxy (—O(SO2)Ph)
85
TMP
TMB
O
O
p-Toluenesulfonyloxy (—O(SO2)Ph-4-CH3)
86
TMP
TMB
O
O
Dodecylbenzenesulfonyloxy
87
TMP
TMB
O
O
p-Bromobenzenesulfonyloxy
(—O(SO2)Ph-4-Br)
88
TMP
TMB
O
O
Diethyl(2-hydroxyethyl)ammonium
89
TMP
TMB
O
O
Benzyldiethylammonium
90
TMP
TMB
O
O
Tris(2-hydroxyethyl)ammonium
91
TMP
TMB
O
O
Dimethyl(2-hydroxyethyl)ammonium
92
TMP
TMB
O
O
Benzyldimethylammonium
93
TMP
TMB
O
O
Trimethylammonium
94
DMP
Ph
O
O
Cl
95
DMP
Ph
O
O
I
96
DMP
Ph
O
O
OCN
97
DMP
Ph
O
O
SCN
98
DMP
Ph
O
O
CN
99
DMP
Ph
O
O
Acetoxy (—O(CO)CH3)
100
DMP
Ph
O
O
Benzoyloxy (—O(CO)Ph)
101
DMP
Ph
O
O
Formyloxy (—O(CO)H)
102
DMP
Ph
O
O
Methoxycarbonyloxy (—O(CO)OCH3)
103
DMP
Ph
O
O
Ethoxycarbonyloxy (—O(CO)OCH2CH3)
104
DMP
Ph
O
O
n-Butoxycarbonyloxy (—O(CO)OCH2CH2CH2CH3)
105
DMP
Ph
O
O
Chlorocarbonyloxy (—O(CO)Cl)
106
DMP
Ph
O
O
Chlorosulfinyloxy (—O(SO)Cl)
107
DMP
Ph
O
O
Methoxysulfinyloxy (—O(SO)OCH3)
108
DMP
Ph
O
O
Ethoxysulfinyloxy (—O(SO)OCH2CH3)
109
DMP
Ph
O
O
n-Butoxysulfinyloxy (—O(SO)OCH2CH2CH2CH3)
110
DMP
Ph
O
O
Chlorosulfuryloxy (—O(SO2)Cl)
111
DMP
Ph
O
O
Methoxysulfuryloxy (—O(SO2)OCH3)
112
DMP
Ph
O
O
Ethoxysulfuryloxy (—O(SO2)OCH2CH3)
113
DMP
Ph
O
O
Methylsulfonyloxy (—O(SO2)CH3)
114
DMP
Ph
O
O
Trifluoromethylsulfonyloxy (—O(SO2)CF3)
115
DMP
Ph
O
O
Benzenesulfonyloxy (—O(SO2)Ph)
116
DMP
Ph
O
O
p-Toluenesulfonyloxy (—O(SO2)Ph-4-CH3)
117
DMP
Ph
O
O
Dodecylbenzenesulfonyloxy
118
DMP
Ph
O
O
p-Bromobenzenesulfonyloxy
(—O(SO2)Ph-4-Br)
119
DMP
Ph
O
O
Diethyl(2-hydroxyethyl)ammonium
120
DMP
Ph
O
O
Benzyldiethylammonium
121
DMP
Ph
O
O
Tris(2-hydroxyethyl)ammonium
122
DMP
Ph
O
O
Dimethyl(2-hydroxyethyl)ammonium
123
DMP
Ph
O
O
Benzyldimethylammonium
124
DMP
Ph
O
O
Trimethylammonium
125
DMP
OEt
O
O
Cl
126
DMP
OEt
O
O
I
127
DMP
OEt
O
O
OCN
128
DMP
OEt
O
O
SCN
129
DMP
OEt
O
O
CN
130
DMP
OEt
O
O
Acetoxy (—O(CO)CH3)
131
DMP
OEt
O
O
Benzoyloxy (—O(CO)Ph)
132
DMP
OEt
O
O
Formyloxy (—O(CO)H)
133
DMP
OEt
O
O
Methoxycarbonyloxy (—O(CO)OCH3)
134
DMP
OEt
O
O
Ethoxycarbonyloxy (—O(CO)OCH2CH3)
135
DMP
OEt
O
O
n-Butoxycarbonyloxy (—O(CO)OCH2CH2CH2CH3)
136
DMP
OEt
O
O
Chlorocarbonyloxy (—O(CO)Cl)
137
DMP
OEt
O
O
Chlorosulfinyloxy (—O(SO)Cl)
138
DMP
OEt
O
O
Methoxysulfinyloxy (—O(SO)OCH3)
139
DMP
OEt
O
O
Ethoxysulfinyloxy (—O(SO)OCH2CH3)
140
DMP
OEt
O
O
n-Butoxysulfinyloxy (—O(SO)OCH2CH2CH2CH3)
141
DMP
OEt
O
O
Chlorosulfuryloxy (—O(SO2)Cl)
142
DMP
OEt
O
O
Methoxysulfuryloxy (—O(SO2)OCH3)
143
DMP
OEt
O
O
Ethoxysulfuryloxy (—O(SO2)OCH2CH3)
144
DMP
OEt
O
O
Methylsulfonyloxy (—O(SO2)CH3)
145
DMP
OEt
O
O
Trifluoromethylsulfonyloxy (—O(SO2)CF3)
146
DMP
OEt
O
O
Benzenesulfonyloxy (—O(SO2)Ph)
147
DMP
OEt
O
O
p-Toluenesulfonyloxy (—O(SO2)Ph-4-CH3)
148
DMP
OEt
O
O
Dodecylbenzenesulfonyloxy
149
DMP
OEt
O
O
p-Bromobenzenesulfonyloxy
(—O(SO2)Ph-4-Br)
150
DMP
OEt
O
O
Diethyl(2-hydroxyethyl)ammonium
151
DMP
OEt
O
O
Benzyldiethylammonium
152
DMP
OEt
O
O
Tris(2-hydroxyethyl)ammonium
153
DMP
OEt
O
O
Dimethyl(2-hydroxyethyl)ammonium
154
DMP
OEt
O
O
Benzyldimethylammonium
155
DMP
OEt
O
O
Trimethylammonium
156
DMP
TMB
O
O
Cl
157
DMP
TMB
O
O
I
158
DMP
TMB
O
O
OCN
159
DMP
TMB
O
O
SCN
160
DMP
TMB
O
O
CN
161
DMP
TMB
O
O
Acetoxy (—O(CO)CH3)
162
DMP
TMB
O
O
Benzoyloxy (—O(CO)Ph)
163
DMP
TMB
O
O
Formyloxy (—O(CO)H)
164
DMP
TMB
O
O
Methoxycarbonyloxy (—O(CO)OCH3)
165
DMP
TMB
O
O
Ethoxycarbonyloxy (—O(CO)OCH2CH3)
166
DMP
TMB
O
O
n-Butoxycarbonyloxy (—O(CO)OCH2CH2CH2CH3)
167
DMP
TMB
O
O
Chlorocarbonyloxy (—O(CO)Cl)
168
DMP
TMB
O
O
Chlorosulfinyloxy (—O(SO)Cl)
169
DMP
TMB
O
O
Methoxysulfinyloxy (—O(SO)OCH3)
170
DMP
TMB
O
O
Ethoxysulfinyloxy (—O(SO)OCH2CH3)
171
DMP
TMB
O
O
n-Butoxysulfinyloxy (—O(SO)OCH2CH2CH2CH3)
172
DMP
TMB
O
O
Chlorosulfuryloxy (—O(SO2)Cl)
173
DMP
TMB
O
O
Methoxysulfuryloxy (—O(SO2)OCH3)
174
DMP
TMB
O
O
Ethoxysulfuryloxy (—O(SO2)OCH2CH3)
175
DMP
TMB
O
O
Methylsulfonyloxy (—O(SO2)CH3)
176
DMP
TMB
O
O
Trifluoromethylsulfonyloxy (—O(SO2)CF3)
177
DMP
TMB
O
O
Benzenesulfonyloxy (—O(SO2)Ph)
178
DMP
TMB
O
O
p-Toluenesulfonyloxy (—O(SO2)Ph-4-CH3)
179
DMP
TMB
O
O
Dodecylbenzenesulfonyloxy
180
DMP
TMB
O
O
p-Bromobenzenesulfonyloxy
(—O(SO2)Ph-4-Br)
181
DMP
TMB
O
O
Diethyl(2-hydroxyethyl)ammonium
182
DMP
TMB
O
O
Benzyldiethylammonium
183
DMP
TMB
O
O
Tris(2-hydroxyethyl)ammonium
184
DMP
TMB
O
O
Dimethyl(2-hydroxyethyl)ammonium
185
DMP
TMB
O
O
Benzyldimethylammonium
186
DMP
TMB
O
O
Trimethylammonium
187
DMOP
Ph
O
O
Cl
188
DMOP
Ph
O
O
I
189
DMOP
Ph
O
O
OCN
190
DMOP
Ph
O
O
SCN
191
DMOP
Ph
O
O
CN
192
DMOP
Ph
O
O
Acetoxy (—O(CO)CH3)
193
DMOP
Ph
O
O
Benzoyloxy (—O(CO)Ph)
194
DMOP
Ph
O
O
Formyloxy (—O(CO)H)
195
DMOP
Ph
O
O
Methoxycarbonyloxy (—O(CO)OCH3)
196
DMOP
Ph
O
O
Ethoxycarbonyloxy (—O(CO)OCH2CH3)
197
DMOP
Ph
O
O
n-Butoxycarbonyloxy (—O(CO)OCH2CH2CH2CH3)
198
DMOP
Ph
O
O
Chlorocarbonyloxy (—O(CO)Cl)
199
DMOP
Ph
O
O
Chlorosulfinyloxy (—O(SO)Cl)
200
DMOP
Ph
O
O
Methoxysulfinyloxy (—O(SO)OCH3)
201
DMOP
Ph
O
O
Ethoxysulfinyloxy (—O(SO)OCH2CH3)
202
DMOP
Ph
O
O
n-Butoxysulfinyloxy (—O(SO)OCH2CH2CH2CH3)
203
DMOP
Ph
O
O
Chlorosulfuryloxy (—O(SO2)Cl)
204
DMOP
Ph
O
O
Methoxysulfuryloxy (—O(SO2)OCH3)
205
DMOP
Ph
O
O
Ethoxysulfuryloxy (—O(SO2)OCH2CH3)
206
DMOP
Ph
O
O
Methylsulfonyloxy (—O(SO2)CH3)
207
DMOP
Ph
O
O
Trifluoromethylsulfonyloxy (—O(SO2)CF3)
208
DMOP
Ph
O
O
Benzenesulfonyloxy (—O(SO2)Ph)
209
DMOP
Ph
O
O
p-Toluenesulfonyloxy (—O(SO2)Ph-4-CH3)
210
DMOP
Ph
O
O
Dodecylbenzenesulfonyloxy
211
DMOP
Ph
O
O
p-Bromobenzenesulfonyloxy
(—O(SO2)Ph-4-Br)
212
DMOP
Ph
O
O
Diethyl(2-hydroxyethyl)ammonium
213
DMOP
Ph
O
O
Benzyldiethylammonium
214
DMOP
Ph
O
O
Tris(2-hydroxyethyl)ammonium
215
DMOP
Ph
O
O
Dimethyl(2-hydroxyethyl)ammonium
216
DMOP
Ph
O
O
Benzyldimethylammonium
217
DMOP
Ph
O
O
Trimethylammonium
218
DMOP
OEt
O
O
Cl
219
DMOP
OEt
O
O
I
220
DMOP
OEt
O
O
OCN
221
DMOP
OEt
O
O
SCN
222
DMOP
OEt
O
O
CN
223
DMOP
OEt
O
O
Acetoxy (—O(CO)CH3)
224
DMOP
OEt
O
O
Benzoyloxy (—O(CO)Ph)
225
DMOP
OEt
O
O
Formyloxy (—O(CO)H)
226
DMOP
OEt
O
O
Methoxycarbonyloxy (—O(CO)OCH3)
227
DMOP
OEt
O
O
Ethoxycarbonyloxy (—O(CO)OCH2CH3)
228
DMOP
OEt
O
O
n-Butoxycarbonyloxy (—O(CO)OCH2CH2CH2CH3)
229
DMOP
OEt
O
O
Chlorocarbonyloxy (—O(CO)Cl)
230
DMOP
OEt
O
O
Chlorosulfinyloxy (—O(SO)Cl)
231
DMOP
OEt
O
O
Methoxysulfinyloxy (—O(SO)OCH3)
232
DMOP
OEt
O
O
Ethoxysulfinyloxy (—O(SO)OCH2CH3)
233
DMOP
OEt
O
O
n-Butoxysulfinyloxy (—O(SO)OCH2CH2CH2CH3)
234
DMOP
OEt
O
O
Chlorosulfuryloxy (—O(SO2)Cl)
235
DMOP
OEt
O
O
Methoxysulfuryloxy (—O(SO2)OCH3)
236
DMOP
OEt
O
O
Ethoxysulfuryloxy (—O(SO2)OCH2CH3)
237
DMOP
OEt
O
O
Methylsulfonyloxy (—O(SO2)CH3)
238
DMOP
OEt
O
O
Trifluoromethylsulfonyloxy (—O(SO2)CF3)
239
DMOP
OEt
O
O
Benzenesulfonyloxy (—O(SO2)Ph)
240
DMOP
OEt
O
O
p-Toluenesulfonyloxy (—O(SO2)Ph-4-CH3)
241
DMOP
OEt
O
O
Dodecylbenzenesulfonyloxy
242
DMOP
OEt
O
O
p-Bromobenzenesulfonyloxy
(—O(SO2)Ph-4-Br)
243
DMOP
OEt
O
O
Diethyl(2-hydroxyethyl)ammonium
244
DMOP
OEt
O
O
Benzyldiethylammonium
245
DMOP
OEt
O
O
Tris(2-hydroxyethyl)ammonium
246
DMOP
OEt
O
O
Dimethyl(2-hydroxyethyl)ammonium
247
DMOP
OEt
O
O
Benzyldimethylammonium
248
DMOP
OEt
O
O
Trimethylammonium
249
DMOP
TMB
O
O
Cl
250
DMOP
TMB
O
O
I
251
DMOP
TMB
O
O
OCN
252
DMOP
TMB
O
O
SCN
253
DMOP
TMB
O
O
CN
254
DMOP
TMB
O
O
Acetoxy (—O(CO)CH3)
255
DMOP
TMB
O
O
Benzoyloxy (—O(CO)Ph)
256
DMOP
TMB
O
O
Formyloxy (—O(CO)H)
257
DMOP
TMB
O
O
Methoxycarbonyloxy (—O(CO)OCH3)
258
DMOP
TMB
O
O
Ethoxycarbonyloxy (—O(CO)OCH2CH3)
259
DMOP
TMB
O
O
n-Butoxycarbonyloxy (—O(CO)OCH2CH2CH2CH3)
260
DMOP
TMB
O
O
Chlorocarbonyloxy (—O(CO)Cl)
261
DMOP
TMB
O
O
Chlorosulfinyloxy (—O(SO)Cl)
262
DMOP
TMB
O
O
Methoxysulfinyloxy (—O(SO)OCH3)
263
DMOP
TMB
O
O
Ethoxysulfinyloxy (—O(SO)OCH2CH3)
264
DMOP
TMB
O
O
n-Butoxysulfinyloxy (—O(SO)OCH2CH2CH2CH3)
265
DMOP
TMB
O
O
Chlorosulfuryloxy (—O(SO2)Cl)
266
DMOP
TMB
O
O
Methoxysulfuryloxy (—O(SO2)OCH3)
267
DMOP
TMB
O
O
Ethoxysulfuryloxy (—O(SO2)OCH2CH3)
268
DMOP
TMB
O
O
Methylsulfonyloxy (—O(SO2)CH3)
269
DMOP
TMB
O
O
Trifluoromethylsulfonyloxy (—O(SO2)CF3)
270
DMOP
TMB
O
O
Benzenesulfonyloxy (—O(SO2)Ph)
271
DMOP
TMB
O
O
p-Toluenesulfonyloxy (—O(SO2)Ph-4-CH3)
272
DMOP
TMB
O
O
Dodecylbenzenesulfonyloxy
273
DMOP
TMB
O
O
p-Bromobenzenesulfonyloxy
(—O(SO2)Ph-4-Br)
274
DMOP
TMB
O
O
Diethyl(2-hydroxyethyl)ammonium
275
DMOP
TMB
O
O
Benzyldimethylammonium
276
DMOP
TMB
O
O
Tris(2-hydroxyethyl)ammonium
277
DMOP
TMB
O
O
Dimethyl(2-hydroxyethyl)ammonium
278
DMOP
TMB
O
O
Benzyldimethylammonium
279
DMOP
TMB
O
O
Trimethylammonium
280
DCP
Ph
O
O
Cl
281
DCP
Ph
O
O
I
282
DCP
Ph
O
O
OCN
283
DCP
Ph
O
O
SCN
284
DCP
Ph
O
O
CN
285
DCP
Ph
O
O
Acetoxy (—O(CO)CH3)
286
DCP
Ph
O
O
Benzoyloxy (—O(CO)Ph)
287
DCP
Ph
O
O
Formyloxy (—O(CO)H)
288
DCP
Ph
O
O
Methoxycarbonyloxy (—O(CO)OCH3)
289
DCP
Ph
O
O
Ethoxycarbonyloxy (—O(CO)OCH2CH3)
290
DCP
Ph
O
O
n-Butoxycarbonyloxy (—O(CO)OCH2CH2CH2CH3)
291
DCP
Ph
O
O
Chlorocarbonyloxy (—O(CO)Cl)
292
DCP
Ph
O
O
Chlorosulfinyloxy (—O(SO)Cl)
293
DCP
Ph
O
O
Methoxysulfinyloxy (—O(SO)OCH3)
294
DCP
Ph
O
O
Ethoxysulfinyloxy (—O(SO)OCH2CH3)
295
DCP
Ph
O
O
n-Butoxysulfinyloxy (—O(SO)OCH2CH2CH2CH3)
296
DCP
Ph
O
O
Chlorosulfuryloxy (—O(SO2)Cl)
297
DCP
Ph
O
O
Methoxysulfuryloxy (—O(SO2)OCH3)
298
DCP
Ph
O
O
Ethoxysulfuryloxy (—O(SO2)OCH2CH3)
299
DCP
Ph
O
O
Methylsulfonyloxy (—O(SO2)CH3)
300
DCP
Ph
O
O
Trifluoromethylsulfonyloxy (—O(SO2)CF3)
301
DCP
Ph
O
O
Benzenesulfonyloxy (—O(SO2)Ph)
302
DCP
Ph
O
O
p-Toluenesulfonyloxy (—O(SO2)Ph-4-CH3)
303
DCP
Ph
O
O
Dodecylbenzenesulfonyloxy
304
DCP
Ph
O
O
p-Bromobenzenesulfonyloxy
(—O(SO2)Ph-4-Br)
305
DCP
Ph
O
O
Diethyl(2-hydroxyethyl)ammonium
306
DCP
Ph
O
O
Benzyldiethylammonium
307
DCP
Ph
O
O
Tris(2-hydroxyethyl)ammonium
308
DCP
Ph
O
O
Dimethyl(2-hydroxyethyl)ammonium
309
DCP
Ph
O
O
Benzyldimethylammonium
310
DCP
Ph
O
O
Trimethylammonium
311
DCP
OEt
O
O
Cl
312
DCP
OEt
O
O
I
313
DCP
OEt
O
O
OCN
314
DCP
OEt
O
O
SCN
315
DCP
OEt
O
O
CN
316
DCP
OEt
O
O
Acetoxy (—O(CO)CH3)
317
DCP
OEt
O
O
Benzoyloxy (—O(CO)Ph)
318
DCP
OEt
O
O
Formyloxy (—O(CO)H)
319
DCP
OEt
O
O
Methoxycarbonyloxy (—O(CO)OCH3)
320
DCP
OEt
O
O
Ethoxycarbonyloxy (—O(CO)OCH2CH3)
321
DCP
OEt
O
O
n-Butoxycarbonyloxy (—O(CO)OCH2CH2CH2CH3)
322
DCP
OEt
O
O
Chlorocarbonyloxy (—O(CO)Cl)
323
DCP
OEt
O
O
Chlorosulfinyloxy (—O(SO)Cl)
324
DCP
OEt
O
O
Methoxysulfinyloxy (—O(SO)OCH3)
325
DCP
OEt
O
O
Ethoxysulfinyloxy (—O(SO)OCH2CH3)
326
DCP
OEt
O
O
n-Butoxysulfinyloxy (—O(SO)OCH2CH2CH2CH3)
327
DCP
OEt
O
O
Chlorosulfuryloxy (—O(SO2)Cl)
328
DCP
OEt
O
O
Methoxysulfuryloxy (—O(SO2)OCH3)
329
DCP
OEt
O
O
Ethoxysulfuryloxy (—O(SO2)OCH2CH3)
330
DCP
OEt
O
O
Methylsulfonyloxy (—O(SO2)CH3)
331
DCP
OEt
O
O
Trifluoromethylsulfonyloxy (—O(SO2)CF3)
332
DCP
OEt
O
O
Benzenesulfonyloxy (—O(SO2)Ph)
333
DCP
OEt
O
O
p-Toluenesulfonyloxy (—O(SO2)Ph-4-CH3)
334
DCP
OEt
O
O
Dodecylbenzenesulfonyloxy
335
DCP
OEt
O
O
p-Bromobenzenesulfonyloxy
(—O(SO2)Ph-4-Br)
336
DCP
OEt
O
O
Diethyl(2-hydroxyethyl)ammonium
337
DCP
OEt
O
O
Benzyldiethylammonium
338
DCP
OEt
O
O
Tris(2-hydroxyethyl)ammonium
339
DCP
OEt
O
O
Dimethyl(2-hydroxyethyl)ammonium
340
DCP
OEt
O
O
Benzyldimethylammonium
341
DCP
OEt
O
O
Trimethylammonium
342
DCP
TMB
O
O
Cl
343
DCP
TMB
O
O
I
344
DCP
TMB
O
O
OCN
345
DCP
TMB
O
O
SCN
346
DCP
TMB
O
O
CN
347
DCP
TMB
O
O
Acetoxy (—O(CO)CH3)
348
DCP
TMB
O
O
Benzoyloxy (—O(CO)Ph)
349
DCP
TMB
O
O
Formyloxy (—O(CO)H)
350
DCP
TMB
O
O
Methoxycarbonyloxy (—O(CO)OCH3)
351
DCP
TMB
O
O
Ethoxycarbonyloxy (—O(CO)OCH2CH3)
352
DCP
TMB
O
O
n-Butoxycarbonyloxy (—O(CO)OCH2CH2CH2CH3)
353
DCP
TMB
O
O
Chlorocarbonyloxy (—O(CO)Cl)
354
DCP
TMB
O
O
Chlorosulfinyloxy (—O(SO)Cl)
355
DCP
TMB
O
O
Methoxysulfinyloxy (—O(SO)OCH3)
356
DCP
TMB
O
O
Ethoxysulfinyloxy (—O(SO)OCH2CH3)
357
DCP
TMB
O
O
n-Butoxysulfinyloxy (—O(SO)OCH2CH2CH2CH3)
358
DCP
TMB
O
O
Chlorosulfuryloxy (—O(SO2)Cl)
359
DCP
TMB
O
O
Methoxysulfuryloxy (—O(SO2)OCH3)
360
DCP
TMB
O
O
Ethoxysulfuryloxy (—O(SO2)OCH2CH3)
361
DCP
TMB
O
O
Methylsulfonyloxy (—O(SO2)CH3)
362
DCP
TMB
O
O
Trifluoromethylsulfonyloxy (—O(SO2)CF3)
363
DCP
TMB
O
O
Benzenesulfonyloxy (—O(SO2)Ph)
364
DCP
TMB
O
O
p-Toluenesulfonyloxy (—O(SO2)Ph-4-CH3)
365
DCP
TMB
O
O
Dodecylbenzenesulfonyloxy
366
DCP
TMB
O
O
p-Bromobenzenesulfonyloxy
(—O(SO2)Ph-4-Br)
367
DCP
TMB
O
O
Diethyl(2-hydroxyethyl)ammonium
368
DCP
TMB
O
O
Benzyldiethylammonium
369
DCP
TMB
O
O
Tris(2-hydroxyethyl)ammonium
370
DCP
TMB
O
O
Dimethyl(2-hydroxyethyl)ammonium
371
DCP
TMB
O
O
Benzyldimethylammonium
372
DCP
TMB
O
O
Trimethylammonium
TMP: 2,4,6-trimethyl-1-phenyl
DMP: 2,6-dimethyl-1-phenyl
DMOP: 2,6-dimethoxy-1-phenyl
DCP: 2,6-dichloro-1-phenyl
TMB: 2,4,6-trimethylbenzoyl
Ph: phenyl
EtO: ethoxy
As stated above, preference is also given to the species from the table in which R2 is 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl, methoxy, n-propoxy, iso-propoxy, n-butoxy, sec-butoxy, iso-butoxy or tert-butoxy.
As stated above, preference is also given to the species from the table in which R1 is ortho-substituted, for example 2-methylphenyl, 2-methoxyphenyl or 2-chlorophenyl.
The acyl- and bisacylphosphine derivatives (I) according to the invention can be prepared by a process in which a substance of the formula (II)
##STR00005##
where R1, R2, Y and Z are as defined above, and
X is hydrogen or a cation,
is reacted with at least one agent which converts the —OX group into an —FG group.
Cations here can be, for example, those as listed in EP-A 62 839, i.e. equivalents of a cation from main group 1 to 3 of the Periodic Table having a molecular weight of less than 138, or ammonium ions derived from quaternary ammonium ions or triethylenediammonium ions.
Agents which convert the —OX group into the —FG group are known per se to the person skilled in the art. Examples which may be mentioned are phosgene (COCl2), thionyl chloride (SOCl2), sulfuryl chloride (SO2Cl2), phosphorus trichloride (PCl3), phosphorus oxide trichloride (POCl3), phosphorus pentachloride (PCl5), oxalyl chloride ((COCl)2), hydrogen chloride (HCl), chlorine gas (Cl2), N-chloro compounds, for example N-chlorosuccinimide, alkali metal fluorides, cobalt(III) fluoride, halogen fluorides, antimony fluorides, molybdenum fluoride, hydrogen fluoride, hydrogen fluoride/pyridine mixtures, xenon fluorides and other noble-gas compounds, gaseous fluorine, sulfur tetrafluoride, iodine, iodine monochloride, phosphorus triiodide, acid iodides, N-iodosuccinimide, N-iodoacetamide, cyanogen chloride (ClCN), cyanuric chloride (2,4,6-trichloro-1,3,5-triazine, C3Cl3N3), acid chlorides (R5(CO)Cl), esters or anhydrides (R5(CO)2O), carbonic acid chlorides (R5O(CO)Cl), carbonates ((R5O)2(CO)), sulfonic acid chlorides (R5SO2Cl) or sulfonic anhydrides ((R5SO2)2O).
If, furthermore, it is intended to prepare a compound where FG=Br, suitable agents can be, for example: bromine, alkali metal hypobromite, bromine iodide, cyanogen bromide, PBr3, PBr5, POBr3, SOBr2, N-bromosuccinimide, N-bromoacetamide and 1,3-dibromo-5,5-dimethylhydantoin.
If the leaving group FG also contains a reactive center, as in the case of the reaction with phosgene, thionyl chloride, sulfuryl chloride, oxalyl chloride, etc., it is possible to react this reactive center again, for example with an alcohol R5OH, so that —(CO)Cl, —(SO)Cl, —(SO2)Cl groups, etc., are converted into —(CO)OR5, —(SO)OR5 or —(SO2)OR5 groups respectively.
It is furthermore also possible, instead of an —OX group, to convert an —NH2, —NHR6 or —NR6R7 group into an —N+R6R7R8 group by quaternization. This is possible, for example, by reaction with methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, benzyl chloride, dimethyl sulfate, diethyl sulfate, dimethyl carbonate, dibutyl carbonate, ethylene oxide or propylene oxide.
The performance of the reaction for conversion of the —OX group into the —FG group using the above-mentioned agents is known per se to the person skilled in the art and is described, for example, in Organikum—Organisch-chemisches Grundpraktikum, 17th Edition, Berlin, 1988, VEB Deutscher Verlag der Wissenschaften, on pages 189 to 191 (thionyl chloride, phosphorus chlorides and iodine/phosphorus) and 559 (p-toluenesulfonic acid esters), or in Houben-Weyl, Methoden der Organischen Chemie, 4th Edition, 1955, Thieme Verlag, Stuttgart, Ed. Eugen Müller, Volume 9, pages 663 to 668 and 671 to 673 (sulfonic acid esters).
For the reaction with thionyl chloride or R5(SO)Cl, the substrate to be reacted, if desired dissolved in a suitable solvent, for example benzene, toluene, xylene, tetrahydrofuran, hexane, heptane, pentane or petroleum ether, is usually initially introduced in the presence of from 0.9 to 1.5 mol equivalents of an acid scavenger, such as pyridine or a tertiary amine, for example triethylamine, tributylamine, benzyldimethylamine, dimethylaminopyridine, etc., at temperatures between 0° C. and 100° C., preferably between 10° C. and 80° C., and the agent is added with vigorous mixing over a period of from a few minutes to several hours, preferably from 10 to 300 minutes, particularly preferably from 30 to 180 minutes. Stirring can be continued if desired, for example for from 30 to 600 minutes, preferably from 60 to 300 minutes, during which the reaction temperature can slowly be raised in steps.
The resultant reaction product can be processed further in crude or purified form.
If further use in pure form is desired, the product can be purified, for example, by crystallization and solid/liquid separation or by distillation or rectification under reduced pressure.
The yields are generally greater than 75%, usually greater than 80% and frequently greater than 90%.
For the preparation of a group FG=Cl, preference is given to the use of phosgene, thionyl chloride or sulfuryl chloride, particularly preferably phosgene or thionyl chloride and in particular thionyl chloride.
For the preparation of a group FG=OSO2R5, preference is given to the use of R5SO2Cl or (R5SO2)2O, particularly preferably R5SO2Cl.
The compounds of the formula (II) can be obtained as described in EP-A 62 839: a phosphinic acid ester (III), preferably a methyl, ethyl or n-butyl ester, prepared, for example, as mentioned at the outset, can be reacted with a metal halide (MeHal), for example LiCl, LiBr, LiI, NaCl, NaBr, NaI, KCl, KBr or KI, to give the compound (II), where X corresponds to the metal (Me) used. Acidification, for example using sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid or sulfonic acids, or metal exchange with ion exchangers gives the compound (II) where X=H.
##STR00006##
The present invention furthermore relates to a novel process for the preparation of compounds of the formula (II) where X=H in which compounds of the formula (III) are reacted with a halide which is a constituent of an ionic liquid.
The term ionic liquids here is taken to mean ionic compounds which are liquid under the reaction conditions and/or work-up conditions. The melting points of the preferred ionic liquids are generally below 160° C., particularly preferably below 100° C. and very particularly preferably below 80° C.
In the formula (III), R is as defined above for C1-C18-alkyl which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, preferably methyl, ethyl or n-butyl. R1, R2, Y and Z are as defined above.
The term halides here is taken to mean fluoride, chloride, bromide or iodide, preferably bromide or chloride and particularly preferably chloride.
Compounds of this type which can be employed as bases can contain phosphorus, sulfur or nitrogen atoms, for example at least one nitrogen atom, preferably from one to ten nitrogen atoms, particularly preferably from one to five nitrogen atoms, very particularly preferably from one to three nitrogen atoms and in particular one or two nitrogen atoms. If desired, further heteroatoms, for example oxygen, sulfur, phosphorus or halogen atoms, may also be present.
Preference is given to compounds which contain at least one five- to six-membered heterocyclic radical which contains at least one nitrogen atom and, if desired, an oxygen or sulfur atom, particularly preferably compounds which contain at least one five- to six-membered heterocyclic radical which contains one, two or three nitrogen atoms or one nitrogen atom and one oxygen atom, very particularly preferably those containing two nitrogen atoms.
Particularly preferred compounds are those which have a molecular weight of less than 1000 g/mol, very particularly preferably less than 500 g/mol and in particular less than 250 g/mol.
Particular preference is given to pyridines, pyridazines, pyrimidines, pyrazines, imidazoles, 1H-pyrazoles, 3H-pyrazoles, 4H-pyrazoles, 1-pyrazolines, 2-pyrazolines, 3-pyrazolines, imidazolines, thiazoles, oxazoles, 1,2,4-triazoles or 1,2,3-triazoles, of which the pyridines and imidazoles are preferred.
The very particularly preferred bases are 3-chloropyridine, 4-dimethylaminopyridine, 2-ethyl-4-aminopyridine, 2-methylpyridine, 2-ethylpyridine, 2-ethyl-6-methylpyridine, quinoline, isoquinoline, pyridine, 1-C1-C4-alkylimidazole, 1-methylimidazole, 1,2-dimethylimidazole, 1-n-butylimidazole, 1,4,5-trimethylimidazole, 1,4-dimethylimidazole, imidazole, 2-methylimidazole, 1-butyl-2-methylimidazole, 4-methylimidazole, 1-n-pentylimidazole, 1-n-hexylimidazole, 1-n-octylimidazole, 1-(2′-aminoethyl)imidazole, 2-ethyl-4-methylimidazole, 1-vinylimidazole, 2-ethylimidazole, 1-(2′-cyanoethyl)imidazole and benzotriazole.
Particular preference is given to 1-n-butylimidazole, 1-methylimidazole, 2-methylpyridine and 2-ethylpyridine.
To this end, the compound of the formula (III) is reacted with a halide dissolved in an ionic liquid, giving the salt of the said base with the acid (III) where X=H.
This generally requires temperatures of 40-160° C., preferably 50-150° C., particularly preferably 60-140° C., very particularly preferably 80-130° C. and in particular 90-120° C.
The reaction is preferably carried out in the presence of a gas which is inert under the reaction conditions; this is particularly preferably passed through the reaction mixture.
In a further embodiment, a slight reduced pressure is applied, for example 200-900 mbar, preferably 300-800 mbar and particularly preferably 500-750 mbar, in order to simplify separation of the alkyl halide formed.
The reaction mixture can subsequently be diluted with water and the acid (III) liberated using a suitable strong acid, for example sulfuric acid, hydrochloric acid, hydrobromic acid, nitric acid, formic acid or acetic acid, preferably with the strong acid which corresponds to the halide employed.
The acid (III) where X═H can subsequently be separated off by solid-liquid or liquid-liquid separation and, if necessary, purified further.
The acyl- and bisacylphosphine derivatives according to the invention can be used as photoinitiators for the radiation curing of photopolymerizable compositions, for example coating compositions, surface coatings, printing inks, recording materials, aqueous solutions, dispersions and emulsions.
The photoinitiators according to the invention can of course also be used in the form of a mixture with other photoinitiators. These can be, for example, photoinitiators known to the person skilled in the art, for example those mentioned in “Advances in Polymer Science”, Volume 14, Springer Berlin, 1974, or in K. K. Dietliker, Chemistry and Technology of UV- and EB-Formulation for Coatings, Inks and Paints, Volume 3; Photoinitiators for Free Radical and Cationic Polymerization, P. K. T. Oldring (Eds), SITA Technology Ltd, London.
Suitable are, for example, mono- or bisacylphosphine oxides as described, for example, in EP-A 7 508, EP-A 57 474, DE-A 196 18 720, EP-A 495 751 or EP-A 615 980, for example 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin® TPO from BASF AG), ethyl 2,4,6-trimethylbenzoylphenyl phosphinate (Lucirin® TPO L from BASF AG), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Irgacure® 819 from Ciba Spezialitätenchemie), benzophenones, hydroxyacetophenones, phenylglyoxylic acid and derivatives thereof, or mixtures of these photoinitiators. Examples which may be mentioned are benzophenone, acetophenone, acetonaphthoquinone, methyl ethyl ketone, valerophenone, hexanophenone, α-phenylbutyrophenone, p-morpholinopropiophenone, dibenzosuberone, 4-morpholinobehzophenone, 4-morpholinodeoxybenzoin, p-diacetylbenzene, 4-aminobenzophenone, 4′-methoxyacetophenone, β-methylanthraquinone, tert-butylanthraquinone, anthraquinonecarboxylic acid esters, benzaldehyde, α-tetralone, 9-acetylphenanthrene, 2-acetylphenanthrene, 10-thioxanthenone, 3-acetylphenanthrene, 3-acetylindole, 9-fluorenone, 1-indanone, 1,3,4-triacetylbenzene, thioxanthen-9-one, xanthen-9-one, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-di-iso-propylthioxanthone, 2,4-dichlorothioxanthone, benzoin, benzoin iso-butyl ether, chloroxanthenone, benzoin tetrahydropyranyl ether, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, benzoin iso-propyl ether, 7H-benzoin methyl ether, benz[de]anthracen-7-one, 1-naphthaldehyde, 4,4′-bis(dimethylamino)benzophenone, 4-phenylbenzophenone, 4-chlorobenzophenone, Michler's ketone, 1-acetonaphthone, 2-acetonaphthone, 1-benzoylcyclohexan-1-ol, 2-hydroxy-2,2-dimethylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, acetophenone dimethyl ketal, o-methoxybenzophenone, triphenylphosphine, tri-o-tolylphosphine, benz[a]anthracene-7,12-dione, 2,2-diethoxyacetophenone, benzil ketals, such as benzil dimethyl ketal, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, anthraquinones, such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone and 2,3-butanedione.
Also suitable are photoinitiators of the phenylglyoxalic acid ester type which have little or no tendency toward yellowing, as described in DE-A 198 26 712, DE-A 199 13 353 or WO 98/33761.
The acyl- and bisacylphosphine derivatives of the formula (I) according to the invention or the compounds prepared by the process according to the invention are particularly suitable as starting compounds for the preparation of novel photoinitiators, for example those described in the German patent applications with the title “Alkoxylated Mono- and Bisacylphosphine Derivatives” and the file reference 102 06 097.5 and the title “Mono- and Bisacylphosphine Derivatives” and the file reference 102 06 096.7 with the application date Feb. 13, 2002.
Preference is given to the reaction of the acyl- and bisacylphosphine derivatives of the formula (I) according to the invention with compounds which themselves carry a (co)polymerizable group and additionally a group which is capable of reaction with the substances of the formula (I) according to the invention.
Through the leaving group FG, the compounds (I) according to the invention can be chemically coupled to compounds which contain, for example, free hydroxyl, amino, monoalkylamino, monoarylamino and/or mercapto groups. These can preferably be compounds which are themselves polymerizable compounds, i.e. carry at least one (co)polymerizable group, or compounds which carry a group which acts as photoinitiator, for example acylphosphine oxides, bisacylphosphine oxides, benzophenones, acetophenones or phenylglyoxylic acid esters, or those which carry reactive groups which are themselves able to interact with a polymer.
Particular preference is given to the reaction with compounds which carry at least one (co)polymerizable group.
(Co)polymerizable groups can be those which have unsaturated bonds, preferably carbon-carbon double bonds.
These can be, for example, free-radical- or cationically polymerizable groups.
Free-radical-(co)polymerizable groups are, for example, isolated ethylenically unsaturated groups, conjugated unsaturated groups, vinyl-aromatic groups, vinylic and vinylidene chloridic groups, N-vinylamides, vinylpyrrolidones, vinyl lactams, vinyl esters, (meth)acrylic esters or acrylonitriles.
Cationically (co)polymerizable groups are, for example, isobutylene units or vinyl ethers.
Compounds of this type which can be reacted with the acyl- and bisacylphosphine derivatives (I) according to the invention can be, for example, monoesters of a,β-unsaturated carboxylic acids, such as acrylic acid, methacrylic acid (abbreviated to “(meth)acrylic acid” in this specification), crotonic acid, itaconic acid, fumaric acid, maleic acid, acrylamidoglycolic acid, methacrylamidoglycolic acid, or vinyl ethers with diols or polyols, which preferably contain from 2 to 20 carbon atoms and at least two hydroxyl groups, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,1-dimethyl-1,2-ethanediol, dipropylene glycol, tetraethylene glycol, pentaethylene glycol, tripropylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-methyl-1,5-pentanediol, 2-ethyl-1,4-butanediol, 1,4-dimethylolcyclohexane, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, ditrimethylolpropane, erythritol, sorbitol, poly-THF having a molecular weight of from 162 to 2000, poly-1,3-propanediol having a molecular weight of from 134 to 400 or polyethylene glycol having a molecular weight of from 238 to 458. It is furthermore also possible to use esters or amides of (meth)acrylic acid with aminoalcohols, for example 2-aminoethanol, 2-(methylamino)ethanol, 3-amino-1-propanol, 1-amino-2-propanol or 2-(2-aminoethoxy)ethanol, 2-mercaptoethanol or polyaminoalkanes, such as ethylenediamine or diethylenetriamine, or vinylacetic acid.
Also suitable are unsaturated polyetherols or polyesterols or polyacrylate-polyols which have a mean OH functionality of from 2 to 10 and preferably have a molecular weight of from 200 to 2000.
Examples of amides of ethylenically unsaturated carboxylic acids with aminoalcohols are hydroxyalkyl(meth)acrylamides, such as N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-hydroxyethylacrylamide, N-hydroxyethylmethacrylamide, 5-hydroxy-3-oxapentyl(meth)acrylamide,
N-hydroxyalkylcrotonamides, such as N-hydroxymethylcrotonamide, or N-hydroxyalkylmaleimides, such as N-hydroxyethylmaleimide.
For the reaction with (I), preference is given to the use of 2-hydroxyethyl(meth)acrylate, 2- or 3-hydroxypropyl(meth)acrylate, 1,4-butanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, glycerol mono- and di(meth)acrylate, trimethylolpropane mono- and di(meth)acrylate, pentaerythritol mono-, di- and tri(meth)acrylate and 4-hydroxybutyl vinyl ether, 2-aminoethyl(meth)acrylate, 2-aminopropyl(meth)acrylate, 3-aminopropyl(meth)acrylate, 4-aminobutyl(meth)acrylate, 6-aminohexyl(meth)acrylate, 2-thioethyl(meth)acrylate, 2-aminoethyl(meth)acrylamide, 2-aminopropyl(meth)acrylamide, 3-aminopropyl(meth)acrylamide, 2-hydroxyethyl(meth)acrylamide, 2-hydroxypropyl(meth)acrylamide or 3-hydroxypropyl(meth)acrylamide. Particular preference is given to 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl acrylate, 1,4-butanediol monoacrylate and 3-(acryloxy)-2-hydroxypropyl methacrylate.
In this way, it is possible to prepare compounds which can be incorporated into the polymer in a polymerization by means of the polymerizable groups, but which, on the other hand, also act as photoinitiators, which significantly reduces the migration capability of the photoinitiators.
The acyl- and bisacylphosphine derivatives of the formula (I) according to the invention exhibit a migration tendency which is generally lower than most conventional acylphosphine oxide compounds, even without reaction with compounds containing polymerizable groups, since they are capable of reacting, through their reactive group FG, with reactive centers in the components which form the radiation-curable compositions, enabling the compounds according to the invention to be bonded, for example, to the binder of the radiation-curable compositions with formation of a chemical bond.
For example, free hydroxyl, amino, monoalkylamino, monoarylamino and/or mercapto groups are capable of functioning as reactive centers in radiation-curable compositions.
Accordingly, the invention also relates to radiation-curable compositions which are obtainable by reaction of at least one acyl- or bisacylphosphine derivative of the formula (I) or prepared by the process according to the invention with a radiation-curable composition containing free hydroxyl, amino, monoalkylamino, monoarylamino and/or mercapto groups.
Suitable radiation-curable compositions comprise, for example, at least one polymerizable compound having one or more (co)polymerizable, ethylenically unsaturated groups and one or more reactive centers.
These can be, for example, urethane, melamine, polyesterol, polyetherol, epoxide or carbonate acrylates, methacrylates or vinyl ethers containing reactive centers.
The preparation of urethane, melamine, polyesterol, polyetherol, epoxide or carbonate acrylates, methacrylates or vinyl ethers of this type is known per se to the person skilled in the art. The number of reactive centers and ethylenically unsaturated groups can be adjusted through suitable mixing of the individual components.
The number average molecular weight Mn of the polymerizable compounds which can be employed is not restricted. It can be, for example, below 20,000, preferably below 15,000, particularly preferably below 10,000 and in particular below 6000.
The polydispersity Mw/Mn, the quotient of the number average molecular weight and the weight average molecular weight of the polymerizable compounds, represents a measure of the molecular weight distribution of the polymerizable compounds and in the ideal case has the value 1, but in practice values below 4.0, in particular below 3.5, are also satisfactory.
The data on the polydispersity and the number average and weight average molecular weights Mn and Mw are based here on gel permeation chromatography measurements, with polystyrene as standard and tetrahydrofuran as eluent. The method is described in Analytiker Taschenbuch, Vol. 4, pages 433 to 442, Berlin, 1984.
The compounds of the formula (I) according to the invention react, after mixing with the radiation-curable composition, with the reactive centers thereof and are thus bound in a migration-resistant manner.
The coating compositions prepared with the incorporable photoinitiators according to the invention are particularly suitable for use in packaging systems, particularly preferably in the foods sector.
Preference is given to compositions which have from 0.005 to 0.5 mol, particularly preferably 0.01-0.3 mol, very particularly preferably 0.05-0.2 mol and in particular 0.07-0.15 mol of hydroxyl groups per 100 g of substance.
Between 0.05 and 1.0 mol, preferably from 0.1 to 0.9 mol, particularly preferably from 0.2 to 0.8 mol, very particularly preferably from 0.25 to 0.75 mol and in particular from 0.3 to 0.5 mol, of the acyl- and bisacylphosphine derivatives of the formula (I) according to the invention are usually used per mol of hydroxyl groups in the radiation-curable composition.
The bonding of the compounds of the formula (I) according to the invention to the reactive centers is generally carried out at a temperature between room temperature and the curing temperature of the radiation-curable composition obtainable in this way. Typical temperatures are 40-120° C., preferably 50-110° C. and particularly preferably 60-100° C.
In the course of the curing or bonding process, the temperature can be kept constant or increased.
The duration of the thermal treatment is generally between a few minutes and several hours, for example from 1 minute to 5 hours, preferably from 2 minutes to 3 hours, particularly preferably from 5 minutes to 2 hours and in particular from 10 minutes to 1 hour.
It has furthermore been found that compounds of the generic formula (I′) known from the prior art can be used as photoinitiators which conform to the formula (I), but contain a different FG group.
FG in the formula (I′) has the following meanings:
FG is —Br, —(NR3)—NR4R9, —(NR3)—OR9 or —SR3 (for Z=S), and
R9 is hydrogen or C1- to C4-alkyl,
where R3 and R4 are as defined above.
Preferred photoinitiators are compounds in which FG=Br or —SR3.
Radiation-curable compositions typically comprise
Typical compositions are, for example,
In specific applications, the proportion of additives (D) which are typical in surface coatings can be up to 90% by weight. In this case, the proportions of the other components are reduced correspondingly.
Compounds (A) can be, for example, the urethane, melamine, polyesterol, polyetherol, epoxide or carbonate acrylates, methacrylates or vinyl ethers mentioned above.
The compounds (A) are preferably vinyl ether or (meth)acrylate compounds, particularly preferably in each case the acrylate compounds, i.e. the derivatives of acrylic acid.
Preferred vinyl ether and (meth)acrylate compounds (A) contain from 2 to 20, preferably from 2 to 10 and very particularly preferably from 2 to 6 copolymerizable, ethylenically unsaturated double bonds.
Particular preference is given to compounds (A) having a content of ethylenically unsaturated double bonds of 0.1-0.7 mol/100 g, very particularly preferably 0.2-0.6 mol/100 g.
Suitable reactive thinners (compounds (B)) are free-radical-polymerizable compounds, preferably radiation-curable compounds containing an ethylenically unsaturated, copolymerizable group, or mixtures thereof.
Mention may be made, for example, of α,β-unsaturated carboxylic acids, C1-C20-alkyl(meth)acrylates, vinylaromatic compounds having up to 20 carbon atoms, vinyl esters of carboxylic acids containing up to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl ethers of alcohols containing from 1 to 10 carbon atoms, and aliphatic hydrocarbons having from 2 to 8 carbon atoms and one or two double bonds.
For the purposes of this specification, the term (meth)acrylic acid is used for acrylic acid and methacrylic acid.
α,β-Unsaturated carboxylic acids which can be used are, for example, acrylic acid, methacrylic acid, maleic acid or monoesters thereof, 3-acryloxypropionic acid, maleic anhydride, fumaric acid or monoesters thereof, or crotonic acid.
Preferred alkyl(meth)acrylates are those containing a C1-C10-alkyl radical, such as methyl methacrylate, methyl acrylate and ethyl acrylate.
Mixtures of the alkyl(meth)acrylates are also particularly suitable.
Vinyl esters of carboxylic acids having from 1 to 20 carbon atoms are, for example, vinyl laurate, vinyl stearate, vinyl propionate and vinyl acetate.
Suitable vinylaromatic compounds are, for example, vinyltoluene, α-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
Examples of nitriles are acrylonitrile and methacrylonitrile.
Examples of suitable vinyl ethers are vinyl methyl ether, vinyl isobutyl ether, vinyl hexyl ether and vinyl octyl ether.
Non-aromatic hydrocarbons having from 2 to 8 carbon atoms and one or two olefinic double bonds which may be mentioned are butadiene, isoprene, as well as ethylene, propylene and isobutylene.
It is also possible to employ N-vinylformamide, N-vinylpyrrolidone and N-vinylcaprolactam.
The additives (D) which are typical in surface coatings can be, for example, antioxidants, oxidation inhibitors, stabilizers, activators (accelerators), fillers, pigments, dyes, degassing agents, luster agents, antistatic agents, flame inhibitors, thickeners, thixotropic agents, flow-control agents, binders, antifoaming agents, fragrances, surface-active agents, viscosity modifiers, plasticizers, tackifying resins (tackifiers), chelating agents or compatibilizers.
The coating of substrates with the radiation-curable compositions is carried out by conventional methods known to the person skilled in the art, in which at least one radiation-curable composition according to the invention, for example in the form of a dispersion or alternatively without a solvent, is applied in the desired thickness to the substrate to be coated, and the volatile constituents of the dispersion are removed, if necessary with heating. This operation can, if desired, be repeated one or more times.
The application to the substrate can be carried out in a known manner, for example by spraying, dipping, knife coating, using an air blade, brushing, rolling or curtain coating. The coating thickness is generally in the range from about 3 to 1000 g/m2 and preferably from 10 to 200 g/m2.
Also disclosed is a process for the coating of substrates in which a coating composition comprising a substance according to the invention, if desired as a surface-coating formulation to which further additives which are typical in surface coatings and/or thermally curable resins have been added, is applied to the substrate, if desired dried, thermally treated at the curing temperature indicated above, and subsequently cured, if desired at temperatures up to the level of the curing temperature, with active radiation under an oxygen-containing atmosphere, for example air, or preferably under an inert gas.
The process for the coating of substrates can also be carried out by, after application of the mixture or surface-coating formulation according to the invention, firstly effecting curing with active radiation under an oxygen-containing atmosphere, for example air, or preferably under an inert gas, and subsequently carrying out a thermal treatment at the curing temperature.
Thermal and radiation curing can of course also be carried out in parallel.
The curing of the films formed on the substrate can, if desired, be carried out exclusively thermally. In general, however, the coatings are cured both by irradiation with high-energy radiation and also thermally.
If desired, if a plurality of layers of the coating composition are applied one on top of the other, thermal and/or radiation curing can be carried out after each coating operation.
Examples of active energy rays are ultraviolet rays, X-rays and electron beams, preferably ultraviolet rays and electron beams.
The coating of substrates can also be carried out as follows:
Steps iv) and iii) can also be carried out in the reverse sequence, i.e. the film can firstly be cured thermally and then with high-energy radiation.
Typical curing temperatures are 40-120° C., preferably 50-110° C. and particularly preferably 60-100° C.
In the course of the curing process, the temperature can be kept constant or increased.
The curing duration is generally between a few minutes and several hours, for example from 1 minute to 5 hours, preferably from 2 minutes to 3 hours, particularly preferably from 5 minutes to 2 hours and in particular from 10 minutes to 1 hour.
Suitable radiation sources for the radiation curing are, for example, mercury low-pressure emitters, medium-pressure emitters or high-pressure emitters and fluorescent tubes, pulsed emitters, metal-halide emitters, xenon lamps, electrode-less discharge lamps, carbon arc lamps, electronic flash devices, which enable radiation curing without a photoinitiator, or excimer emitters. The radiation curing is carried out through exposure to high-energy radiation, i.e. UV radiation or daylight, preferably light having a wavelength in the range from λ=150 to 700 nm, particularly preferably from λ=200 to 500 nm and very particularly preferably from λ=250 to 400 nm, or by irradiation with high-energy electrons (electron beam; from 50 to 1000 keV, preferably from 100 to 500 keV and particularly preferably from 150 to 300 keV) using devices of, for example, the Cockroft-Walton type, van de Graaff type or resonance type. The radiation sources used are, for example, high-pressure mercury vapor lamps, lasers, pulsed lamps (flashlight), halogen lamps or excimer emitters. The radiation dose which is usually sufficient for crosslinking in the case of UV curing is in the range from 80 to 3000 mJ/cm2.
It is of course also possible to employ a plurality of radiation sources for the curing, for example from two to four.
These can also emit in different wavelength ranges.
Since the chromophore of the acylphosphine oxide has an absorption band in the visible wavelength range above 400 nm, the photoinitiators according to the invention can also be employed with a radiation source having a low or even no UV content.
Daylight curing is likewise possible, albeit generally slower than curing with active energy radiation.
Thus, for example, the absorption spectrum of the compound I-1 essentially corresponds to that of Lucirin TPO, it being crucial that the absorption range extends into the region of visible light.
The irradiation can, if desired, also be carried out with exclusion of oxygen, for example under an inert-gas atmosphere. Suitable inert gases are preferably nitrogen, noble gases, carbon dioxide, or combustion gases. The irradiation can furthermore be carried out by masking the coating composition with transparent media. Transparent media are, for example, plastic films, glass or liquids, for example water. Irradiation is particularly preferably carried out in the manner as described in DE-A 199 57 900.
The following examples are intended to explain the invention, but without representing a restriction thereto.
“Parts” here are taken to mean “parts by weight”, unless specified otherwise.
Trimethylbenzoylphenylphosphinic acid sodium salt
644 g of ethyl trimethylbenzoylphenylphosphinate (Lucirin® TPO-L, BASF AG) were initially introduced in 3000 ml of ethyl methyl ketone, and 1.1 equivalents (285 g) of sodium iodide were added to the solution. After 15 minutes, the homogeneous solution was heated to 65° C. and stirred for 24 hours. The yellow precipitate was filtered off with suction and washed with 2×500 ml of petroleum ether. The filter cake was dried at 60° C. under reduced pressure. 530 g (85% of theory) of pale-yellow powder were isolated.
31P-NMR (d6-DMSO): δ (ppm)=10.8 1H-NMR (d6-DMSO): δ (ppm)=2.2 (s, 6H), 2.25 (s, 3H), 6.6 (s, 2H), 7.3 (m, 3H), 7.6 (m, 2H)
Trimethylbenzoylphenylphosphinic acid
401.55 g of the sodium salt from Example 1 were dissolved in 1500 ml of water acidified to pH 1 with 1300 ml of 0.5 molar sulfuric acid. After 1 hour, the crystal batch which had precipitated was filtered off with suction, washed twice with 700 ml of water each time and sucked dry. The filter cake was dried azeotropically with 1500 ml of toluene in a water separator. The clear, pale-yellow toluene solution was evaporated at 50° C., and the acid was recrystallized from 2150 ml of ethyl acetate. The crystals were filtered off with suction at 0°, washed with ethyl acetate and dried at 60° C. under reduced pressure. Weight: 300 g (80% of theory) of pale-yellow crystals.
31P-NMR (d6-DMSO): δ (ppm)=17.4 1H-NMR (d6-DMSO): δ (ppm)=2.1 (s, 6H), 2.3 (s, 3H), 6.7 (s, 2H), 7.35 (m, 2H), 7.6 (m, 1H), 7.75 (m, 2H)
Trimethylbenzoylphenylphosphinyl chloride
250 g of the acid from Example 2 were suspended in 670 ml of toluene and dissolved with 102.6 g of pyridine. 1546 g of thionyl chloride were added dropwise to the reaction mixture at 60° C. over the course of 1 hour. After a post-reaction time of 3 hours, the red-brown emulsion was cooled to 0° C., and the rust-brown crystals were filtered off. The solution which remained was evaporated under reduced pressure.
Product weight: 265 g (91% of theory). 31P-NMR (d6-DMSO): δ (ppm)=28.4 1H-NMR (d6-DMSO): δ (ppm)=1.7 (s, 6H), 1.8 (s, 3H), 6.4 (s, 2H; mesityl-CH), 7.15 (m, 2H), 7.25 (m, 1H), 7.55 (m, 2H)
Reaction with hydroxyethyl acrylate
A solution of 100 ml of toluene, 7.34 g of triethylamine and 19.07 g of the chloride from Example 3 was warmed to 50° C. under a nitrogen atmosphere. 6.01 g of hydroxyethyl acrylate were metered in portions over the course of 30 minutes. The temperature rose to 60° C. After a further two hours at 50° C., the reaction mixture was cooled to room temperature, and 20 ml of deionized water were added. The organic phase was extracted three times with 30 ml of saturated sodium chloride solution each time. The organic phase dried over sodium sulfate was evaporated to dryness, giving 18.52 g of the product as a brownish oil.
Purity 98% (according to HPLC, retention time 7 minutes, HPLC analysis: Kontron Instruments HPLC-Pump 422, Lichrosorb 18 7, Bischoff Chromatography, Shimadzu C-R6A Chromatopac, Mitlon Roy Spectro Monitor 3100 (230 nm), acetonitrile/water/phosphoric acid (ratio 570:430:1) at 1.1 ml/min.); yield 91% of theory, purity according to 31P-NMR 100%.
Preparation of trimethylbenzoylphenylphosphinic acid
17 g of LiCl were dissolved in 250 ml of dimethylformamide in a 2 l stirred flask fitted with internal thermometer and condenser. A solution of 86 g of ethyl trimethylbenzoylphenylphosphinate in 50 ml of DMF was subsequently added dropwise over the course of one hour. The reaction mixture was subsequently stirred overnight at 65° C. 850 ml of ice-water were added dropwise to the mixture, giving a slightly cloudy solution. After warming to 35° C., 450 ml of 0.5 M H2SO4 were added until a pH of 1.5-2 had been reached, whereupon colorless crystals were precipitated. Stirring was continued at 5° C. for one hour. The crystals were filtered off and washed twice with 200 ml of water each time. Drying gave 71.7 g of 98% pure trimethylbenzoylphenylphosphinic acid (HPLC).
Preparation of trimethylbenzoylphenylphosphinic acid
10 g of ethyl trimethylbenzoylphenylphosphinate and 3.75 g of 1-methylimidazole hydrochloride were combined under a nitrogen atmosphere in a 250 ml four-necked flask with Teflon blade stirrer and condenser, and the mixture was stirred at 110° C. for 5.5 hours. The heating source was subsequently removed, 100 ml of ice-water were added dropwise with vigorous stirring, and the mixture was stirred for a further 10 minutes. An organic/aqueous emulsion formed, which was acidified to pH=1 using 35 ml of 0.5 molar sulfuric acid at about 50° C. with vigorous stirring, cooled to 0° C. and stirred for a further 1 hour. The precipitate which formed was filtered off with suction, washed twice with 25 ml of water each time and dried.
The crude product was recrystallized from 40 ml of ethyl acetate and dried. 7.42 g of trimethylbenzoylphenylphosphinic acid were isolated. The content according to HPLC was >98%.
Maase, Matthias, Henne, Andreas, Noe, Ralf
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